3d self-assembled multi-modal carbon-based particle

ABSTRACT

This disclosure provides a composition of matter nucleated from a homogenous nucleation to form a self-assembled binder-less mesoporous carbon-based particle. In some implementations, the composition includes: a plurality of electrically conductive 3D aggregates formed of graphene sheets and sintered together to define a 3D hierarchical open porous structure comprising mesoscale structuring with micron-scale fractal structuring and configured to provide an electrical conduction between contact points of the graphene sheets. A porous arrangement is formed in the 3D hierarchical open porous structure and is arranged to contain a liquid electrolyte configured to provide ion transport through a plurality of interconnected porous channels in the 3D hierarchical open porous structure. A respective porous channel of the plurality of porous channels includes: a first portion configured to provide tunable ion conduits; a second portion configured to facilitate rapid ion transport; and, a third portion configured to at least partially confine active material.

RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 62/926,225, filed on Oct. 25, 2019 and entitled “3D HierarchicalMesoporous Carbon-Based Particles Integrated into a Continuous ElectrodeFilm Layer”; to U.S. Provisional Patent Application No.: 62/942,103,filed on Nov. 30, 2019 and entitled “3D Hierarchical MesoporousCarbon-Based Particles Integrated into a Continuous Electrode FilmLayer”; all of which are hereby incorporated by reference in theirrespective entireties for all purposes.

TECHNICAL FIELD

This disclosure relates generally to a multi-modal three-dimensional(3D) self-assembled assembled binder-less carbon-based particle(including a controlled sp² and sp³ fraction) created from electricallyconductive 3D aggregates of graphene sheets sintered together to form anopen porous scaffold with a hierarchical pore structure; and, morespecifically, where the hierarchical pore structure facilitates rapidion transport that can correspondingly increase and/or enhanceelectrical conductivity through the graphene sheets (and contact pointsthere-between) of carbon-based particle and scaffolds derived therefrom.

DESCRIPTION OF RELATED ART

Advances in the fields of electronics and telecommunications haveenabled consumers to user devices in many new applications. Portableelectronic devices and peripherals have already become commonplace, manyof which rely on battery-supplied power, and continue to increase inpopularity. Filling the electric power consumption demands,batteries—especially rechargeable (also referred to as “secondary”)batteries, have emerged as a universal solution, allowing for seeminglyindefinite portability and convenient continued device usage.

Nevertheless, challenges related to secondary battery performanceregarding lifespan and cyclability have attracted ongoing innovation inlithium-ion (Li-ion) batteries, which use an intercalated Li compound asa formative material at the positive electrode and graphite at thenegative electrode. Li-ion batteries, as opposed to other battery types,have been sought for usage in portable electronic devices due to theirhigh energy density, limited to no memory effect (describing howtraditional nickel-cadmium and nickel-metal hydride rechargeablebatteries lose their ability to store electrical charge over multiplecharge-discharge cycles involving partial discharge), and relatively lowself-discharge. Thus, Li-ion batteries offer many of the benefits foundin primary (non-rechargeable) lithium batteries, including high chargedensity that results in longer useful lifespans, without the concerns ofrapid discharge resulting in overheating, rupture or explosion that maybe encountered in Li batteries due to the highly reactive (andpotentially explosive and/or combustible) nature of Li metal.

To assist ongoing developments in Li ion battery specific capacity,cycle-ability, and power delivery, amorphous carbon has also beenconsidered (in conjunction with Li) as a formative material for Li ionbattery electrodes. Nevertheless, such electrodes continue to sufferfrom a relatively a low electrical conductivity (high charge transferresistance), which, in turn, results in a high polarization or internalpower loss. Conventional amorphous carbon-based anode materials also maytend to give rise to a high irreversible capacity, among creating otherpotential issues.

Moreover, current Li -intercalated carbon-based electrode compositionsor compounds typically include graphene, conductive carbon particles,and binder. In conventional techniques, carbon-based particles are alltypically deposited, such as being dropped into, existing slurry castelectrodes including current collectors made from metal foil such ascopper. Slurry typically is prepared to contain an organic binder orbinder material referred to as NMP (N-methyl-2-pyrrolidone).

Studies have shown that fabricating battery electrodes by casting amixture of active materials, a nonconductive polymer binder, and aconductive additive onto a metal foil current collector can result inelectric or ionic bottlenecks, and poor electrical contacts due torandomly distributed conductive phases of carbon-based particles whenheld together using binders. Such problems are made worse incircumstances where high-capacity electrode materials are employed,where the high stress generated during electrochemical reactionsassociated with normal battery usage disrupts mechanical integrity ofsuch binder systems, ultimately resulting in decreased cycle life ofbatteries.

As a result, a need exists for a carbon-based electrode material thataddresses the aforementioned challenges of Li ion batteries regardingusage of binders to impart structural integrity to secondary batteryelectrodes, and to have other highly desirable features.

SUMMARY

This Summary is provided to introduce in a simplified form a selectionof concepts that are further described below in the DetailedDescription. This Summary is not intended to identify key features oressential features of the claimed subject matter, nor is it intended tolimit the scope of the claimed subject matter.

One innovative aspect of the subject matter described in this disclosurecan be implemented as a composition of matter nucleated from ahomogenous nucleation to form a self-assembled binder-less mesoporouscarbon-based particle. The composition of matter has a plurality ofelectrically conductive three-dimensional (3D) aggregates formed ofgraphene sheets and sintered together to define a 3D hierarchical openporous structure with mesoscale structuring in combination withmicron-scale fractal structuring and configured to provide an electricalconduction between contact points of the graphene sheets. A porousarrangement is formed in the 3D hierarchical open porous structure andis arranged to contain a liquid electrolyte configured to provide iontransport through a plurality of interconnected porous channels in the3D hierarchical open porous structure. A respective porous channel ofthe plurality of porous channels includes a first portion configured toprovide tunable ion conduits; a second portion configured to facilitaterapid ion transport; and, a third portion configured to at leastpartially or temporarily confine active material. In someimplementations, the mesoporous carbon-based particle is configured tobe grown at least in part by a vapor flow stream. In other aspects, thevapor flow stream is configured to be flowed at least in part into avicinity of a plasma. The vapor flow stream can be flowed at a pressurerange between a vacuum and substantially atmospheric pressure.

In some implementations, the mesoporous carbon-based particle isconfigured to be grown from a carbon-based species. The carbon-basedspecies can be configured to be controlled gas-solid reactions undernon-equilibrium conditions. The gas-solid reactions can be affected atleast in part by any one or more of: (1) ionization potentials and/orthermal energy associated with constituents of the carbon-based species;and, (2) kinetic momentum associated with the gas-solid reactions.

In some aspects, the graphene sheets define Li containing structuresthat provide a source for specific capacity of an anode or cathode at arange of between approximately 744 mAh/g and approximately 1,116 mAh/g.Li can be configured to infiltrate and react with the 3D hierarchicalopen porous structure. The tunable ion conduits can be configured forion transport.

In some implementations, the graphene sheets comprise one or more ofsingle layer graphene (SLG), few layer graphene (FLG), or many layergraphene (MLG). The FLG includes between approximately 2 and 15 layersof graphene. The layers of graphene can be configured to be oriented ina stacked configuration.

In some aspects, (1) the first portion has at least one dimension ofapproximately >50 nanometers; (2) the second portion has at least onedimension of in a range of approximately 20 nanometers to approximately50 nanometers; and, (3) the third portion has at least one dimensionless than approximately 4 nanometers.

In some implementations, one or more material properties of themesoporous carbon-based particle are configured to be defined during itssynthesis. One or more dopants can be incorporated into the mesoporouscarbon-based particle. The one or more dopants can be configured toaffect a material property of the mesoporous carbon-based particle. Thematerial property further can include any one or more of an electricalconductivity, a wettability, or an ion conduction. The wettability canbe configured to at least in part be affected by an electric chargeassociated with the mesoporous carbon-based particle.

In some aspects, the plurality of interconnected pores is defined by oneor more dimensions ranging from 1 to 3 nanometers. Any one or more ofthe graphene sheets can range from between approximately 50 and 200nanometers. The 3D hierarchical open porous structure is configured tobe created independent of a binder.

Another innovative aspect of the subject matter described in thisdisclosure can be implemented in a composition comprising athree-dimensional (3D) self-assembled multi-modal mesoporouscarbon-based particle nucleated and grown in a plasma-based vapor flowstream onto a supporting or sacrificial substrate, the 3D self-assembledmulti-modal mesoporous carbon-based particle synthesized with a 3Dhierarchical structure comprising short range, local nano-structuring incombination with long range fractal structuring, the 3D self-assembledmulti-modal mesoporous carbon-based particle comprising: (a) a pluralityof interconnected 3D agglomerations of multiple layers of graphenesheets sintered together to form an open porous scaffold configured tofacilitate electrical conduction between contact points of the graphenesheets; and (b) a plurality of hierarchical pores interspersed with theopen porous scaffold and configured to define a hierarchical porousnetwork that causes rapid lithium (Li) ion diffusion by providing one ormore of a plurality of Li ion diffusion pathways, each of the Li ionpathways having a dimension suitable for facilitating: (1) temporaryconfinement active material; or, (2) facilitating rapid ion transport.

In some implementations, the one or more of the Li ion diffusionpathways include: (1) frameworks defined by a dimension ofapproximately >50 nanometers that provide Li tunable ion conduits; (2)channels defined by a dimension ranging from approximately 20 nanometersto approximately 50 nanometers and that are configured to facilitaterapid Li ion transport; and, (3) textures defined by a dimension <4nanometers for charge accommodation and/or active material confinement.The 3D self-assembled multi-modal mesoporous carbon-based particle canbe configured to be deposited as a contiguous film onto the supportingor sacrificial substrate.

Another innovative aspect of the subject matter described in thisdisclosure can be implemented as a carbon-based particle comprisingelectrically conductive three-dimensional (3D) aggregates formed ofgraphene sheets, the aggregates sintered together to form an open porousscaffold configured to provide electrical conduction via contact pointsof the graphene sheets; and a porous arrangement formed in the openporous scaffold and configured to assist ion transport through aplurality of contiguous pores, each contiguous pore of the plurality ofcontiguous pores including: a first portion configured to providetunable ion conduits; a second portion configured to facilitate rapidion transport; and, a third portion configured to at least partially ortemporarily confine active material. The open porous scaffold can beused in an electrode of a Li ion battery system.

Another innovative aspect of the subject matter described in thisdisclosure can be implemented as a carbon-based particle comprising aplurality of electrically conductive 3D aggregates formed of graphenesheets randomly sintered together to form a 3D hierarchical structurewith mesoscale structuring in combination with micron-scale fractalstructure configured to facilitate electrical conduction between contactpoints of the graphene sheets. A porous arrangement formed in the 3Dhierarchical structure and containing a liquid electrolyte configured tofacilitate ion transport through interconnected pores that define one ormore channels.

In some aspects, a respective channel of the one or more channelsfurther comprises a first portion configured to provide tunable ionconduits; a second portion configured to facilitate rapid ion transport;and, a third portion configured to at least partially or temporarilyconfine active material.

The details of the subject matter described in this disclosure are setforth in the accompanying drawings and the description below. Otherfeatures, aspects, and advantages of the subject matter will becomeapparent from the description, the drawings, and the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentinvention can be understood in detail, a more particular description ofthe invention, briefly summarized above, may be had by reference to theappended drawings. It is to be noted, however, that the appendeddrawings illustrate examples of this disclosure and are therefore not tobe considered limiting of its scope.

FIGS. 1A-J show illustrative schematic representations, at variousmagnification levels, and/or micrographs of a 3D self-assembledbinder-less 3D mesoporous carbon-based particle having tunableelectrical pathways and ionic conduits throughout the thickness thereof,according to some implementations.

FIGS. 2A-B show illustrative diagrams representative of conventional‘composite’ Li-ion battery electrodes which consist of a slurry castmixture of active materials, according to some implementations.

FIG. 3A shows a micrograph of an example enlarged section of the 3Dself-assembled binder-less mesoporous carbon-based particle shown inFIGS. 1A-1J, according to some implementations.

FIG. 3B shows an illustrative schematic representation of amulti-layered carbon-based scaffolded structure, each layer comprisingvarious concentrations of the 3D mesoporous carbon-based particles shownin FIGS. 1A-J, deposited on an electrically conductive substrate,according to some implementations.

FIG. 4A shows an illustrative schematic representation of amulti-layered carbon-based scaffolded structure, each layer comprisingvarious concentrations of the 3D mesoporous carbon-based particles shownin FIGS. 1A-J, deposited on an electrically conductive substrate, themulti-layered carbon-based scaffolded structure having lithium metalinfused into nanoscale gaps therein, according to some implementations.

FIG. 4B shows an illustrative schematic representation of a series ofplasma spray torches oriented in a substantially continuous sequenceabove a roll-to-roll (R2R) processing apparatus, where the plasma spraytorches are configured to grow the 3D mesoporous carbon-based particlesin an incremental layer-by-layer manner, according to someimplementations.

FIG. 5 shows an example schematic for a traditional Li ion battery inwhich the 3D self-assembled binder-less mesoporous carbon-based particleshown in FIGS. 1A-1J may be incorporated, according to someimplementations.

FIG. 6 shows an example schematic of an artificial solid-electrolytefilm enhanced by doping (with metal powder), according to someimplementations.

FIGS. 7A-B show various photographs and/or micrographs related ofexample variants of the 3D mesoporous carbon-based particles shown inFIGS. 1A-J, according to some implementations.

FIG. 8A shows an enlarged portion of the 3D mesoporous carbon-basedparticles shown in FIGS. 1A-J, according to some implementations.

FIG. 8B shows the enlarged portion of the 3D mesoporous carbon-basedparticles shown in FIGS. 1A-J with graphene-on-graphene densification,according to some implementations.

FIGS. 9A-E shows various images of carbon and/or graphene and carbonparticle-based 3D structures, including real-life representations ofthat shown by the 3D mesoporous carbon-based particles shown in FIGS.1A-J, with high degrees of purity and tunability, according to someimplementations.

FIG. 10A shows a planning diagram representative of traditionalsilicon-chip based manufacturing techniques and related information,according to some implementations.

FIG. 10B shows a planning diagram representative of advanced 3D grapheneand/or carbon-based industry-focused applications and/or solutions,according to some implementations.

FIG. 11 shows graphene and/or 3D graphene-based particles and/orfew-layer graphene (FLG) associated with the 3D mesoporous carbon-basedparticles shown in FIGS. 1A-J, according to some implementations.

FIG. 12 shows a listing of properties associated with the 3D mesoporouscarbon-based particles shown in FIGS. 1A-J, according to someimplementations.

FIG. 13 shows various charts, equipment, and particle products of carbonand/or 3D graphene, according to some implementations.

FIG. 14 shows various depictions of porous innately graphenenano-platelets (GNP) connected particle products and/or FLG and relatedequipment, according to some implementations.

FIG. 15 shows a schematic example representation of the 3D mesoporouscarbon-based particles shown in FIGS. 1A-J featuring sulfurmicro-confinement therein, according to some implementations.

FIG. 16 shows the 3D mesoporous carbon-based particles shown in FIGS.1A-J with Li intercalation between graphene layers, according to someimplementations.

FIG. 17 shows a listing of properties and/or features associated withintegrated 3D scaffolded films formed at least in part by the 3Dmesoporous carbon-based particles shown in FIGS. 1A-J, according to someimplementations.

FIG. 18 shows a listing of properties and/or features associated withreactor-to-film processed carbons, according to some implementations.

FIG. 19 shows a general progression of proprietary carbon depositionassociated with the 3D mesoporous carbon-based particles shown in FIGS.1A-J, carbon-based materials being deposited on a substrate byroll-to-roll (R2R) processing, according to some implementations.

FIG. 20 shows a listing of features of the 3D mesoporous carbon-basedparticles shown in FIGS. 1A-J that enable significant batteryperformance advantages over currently available Li-ion batteries,according to some implementations.

FIG. 21 shows various images of a sulfur cathode and a Li-S systemperformance chart over cycles, according to some implementations.

FIG. 22 shows cathode specific capacity levels over cycles and variousrepresentative sulfur-nano confinement diagrams and images, according tosome implementations.

FIG. 23 shows various images, tables and charts regarding acceleratedcarbon tuning achieved by at least partially incorporating the 3Dself-assembled binder-less mesoporous carbon-based particle shown inFIGS. 1A-1J into a battery electrode to mitigate polysulfide relatedissues, according to some implementations.

FIG. 24 shows a chart of example battery capacity retention values forinfusion and/or incorporation of sulfur and/or lithium in the 3Dself-assembled binder-less mesoporous carbon-based particle shown inFIGS. 1A-1J with relation to battery capacity and stability, accordingto some implementations.

FIG. 25 shows spectroscopic images revealing uniform distribution ofsulfur in the 3D self-assembled binder-less mesoporous carbon-basedparticle shown in FIGS. 1A-1J, according to some implementations.

FIG. 26 shows a chart for specific capacity (mAh/g) vs. percentage ofsulfur (thermo-gravimetric analysis value; TGA) for the 3Dself-assembled binder-less mesoporous carbon-based particle shown inFIGS. 1A-1J, according to some implementations.

FIG. 27 shows a graph of percentage battery electric storage capacityretention over cycles for the 3D self-assembled binder-less mesoporouscarbon-based particle shown in FIGS. 1A-1J, according to someimplementations.

FIG. 28 shows a listing of various battery-related industry challenges,according to some implementations.

FIG. 29A-N show various proprietary approaches concerning apre-lithiated carbon host structure and/or active Li ion intercalatingstructures for the 3D self-assembled binder-less mesoporous carbon-basedparticle shown in FIGS. 1A-1J, according to some implementations.

FIG. 30 shows Raman spectra for 3D N-doped FL graphene includingcharting for both pristine carbon and N-doped carbon, according to someimplementations.

FIG. 31 shows a listing of reactor tuning parameters and/or properties,according to some implementations.

FIG. 32 shows various properties associated with bilayer graphene,according to some implementations.

FIG. 33 shows a method for preparing a 3D scaffolded film containingcarbon-based particles, according to some implementations.

To facilitate understanding, identical reference numerals have beenused, where possible, to designate identical elements that are common tothe figures. It is contemplated that elements disclosed may bebeneficially utilized on other elements without specific recitation. Thedrawings referred to here should not be understood as being drawn toscale unless specifically noted. Also, the drawings are oftensimplified, and details or components omitted for clarity ofpresentation and explanation. The drawings and discussion serve toexplain principles discussed below, where like designations denote likeelements.

DETAILED DESCRIPTION

Various aspects of the novel systems, apparatuses, and methods aredescribed more fully herein with reference to the accompanying drawings.The teachings disclosed can, however, be embodied in many differentforms and should not be construed as limited to any specific structureor function presented throughout this disclosure. Rather, these aspectsare provided so that this disclosure will be thorough and complete, andwill fully convey the scope of the disclosure to those skilled in theart.

Based on the teachings herein one skilled in the art should appreciatethat the scope of the disclosure is intended to cover any aspect of thenovel systems, apparatuses, and methods disclosed herein, whetherimplemented independently of or combined with any other aspect of theinvention. For example, an apparatus can be implemented, or a method canbe practiced using any number of the aspects set forth herein. Inaddition, the scope of the invention is intended to cover such anapparatus or method which is practiced using other structure,functionality, or structure and functionality in addition to or otherthan the various aspects of the invention set forth herein. Any aspectdisclosed herein can be embodied by one or more elements of a claim.

Although some examples and aspects are described herein, many variationsand permutations of these examples fall within the scope of thedisclosure. Although some benefits and advantages of the preferredaspects are mentioned, the scope of the disclosure is not intended to belimited to benefits, uses, or objectives. Rather, aspects of thedisclosure are intended to be broadly applicable to a 3D self-assembledmulti-modal mesoporous carbon-based particle composed of electricallyconductive three-dimensional (3D) aggregates of graphene sheets, some ofwhich are illustrated in the figures and in the following description ofthe preferred aspects. The detailed description and drawings are merelyillustrative of the disclosure rather than limiting, the scope of thedisclosure being defined by the appended claims and equivalents thereof.

Definitions Li -Ion Batteries

A Li-ion battery is a type of secondary (rechargeable) battery. Li-ionbattery technology has become very important in recent years as thesebatteries show great promise as power sources that can lead to anelectric vehicle (EV) revolution (referring to widespread implementationof EVs across numerous applications). The development of new materials(for Li-ion batteries) is the focus of research in the field ofmaterials science, as Li-ion batteries can be considered to be the mostimpressive success story of modern electrochemistry. Li-ion batteriespower most modern portable devices and seem to have overcomepsychological barriers of the consuming public against the use of suchhigh energy density devices on a larger scale for more demandingapplications, such as EV.

Regarding operation, in Li-ion batteries, Li ions (Li+) migrate from thenegative electrode through an electrolyte to the positive electrodeduring discharge and return when charging. Li-ion batteriestraditionally use an intercalated Li compound as a formative material atthe positive electrode and graphite at the negative electrode. Thebatteries have a high energy density, no “memory-effect” (describing thesituation in which nickel-cadmium batteries gradually lose their maximumenergy capacity if they are repeatedly recharged after being onlypartially discharged) and low self-discharge. However, unlikeconventional battery chemistries, Li ion batteries can (due to thehighly reactive nature of elemental and ionic Li) present a safetyhazard. Under certain conditions, since Li ion batteries can contain aflammable electrolyte, if they are punctured, hit, otherwise damaged oreven incorrectly (excessively) charged, Li batteries can deteriorateunexpectedly, including through explosions and fires. Nevertheless, thehigh energy density of Li ion batteries permits for longer usablelifespans of several hours between charging cycles, and longer cyclelife, referring to the electric current delivery or output performanceof a given Li -ion battery over multiple repeat charge-discharge(partial or total charge depletion) cycles.

Li metal, due to its high theoretical specific capacity of 3,860 mAh/g,low density (0.59 g cm-3) and low negative electrochemical potential(−3.040 V compared to a standard hydrogen electrode), appears as anideal material for the negative electrode of secondary Li -ionbatteries. However, unavoidable and uncontrollable dendrite growth,referring the growth of a branching tree-like structure within thebattery itself, caused by Li precipitates can cause serious safetyconcerns related to short-circuits, and limited Coulombic efficiency,referring to the charge efficiency by which electrons are transferred inbatteries, during deposition and stripping operations inherent in Li-ion batteries. Such challenges have previously impeded Li ion batteryapplications.

However, concerns related to safety of earlier-developed Li secondarybatteries led to the creation and refinement of newer generation Li-ionsecondary batteries. Such Li-ion batteries typically featurecarbonaceous materials used as an anode, such carbonaceous anodematerials including: (1) graphite; (2) amorphous carbon; and, (3)graphitized carbon. The first type of the three carbonaceous materialspresented above includes naturally occurring graphite and syntheticgraphite (or artificial graphite, such as Highly Oriented PyrolyticGraphite, HOPG). Either form of graphite can be intercalated with Li.The resulting Graphite Intercalation Compound (GIC) may be expressed asLi_(x)C₆, where X is typically less than 1. To limit (minimize) the lossin energy density due to the replacement of Li metal with the GIC, X inLi_(x)C₆ must be maximized and the irreversible capacity loss (Q_(ir)),in the first charge of the battery must be minimized.

The maximum amount of Li that can be reversibly intercalated into theinterstices between graphene planes of a perfect graphite crystal isgenerally believed to occur in a graphite intercalation compoundrepresented by Li_(x)C₆ (x=1), corresponding to a theoretical 372 mAh/g.However, such a limited specific capacity (of the discussed theoretical372 mAh/g) cannot satisfy the demanding requirements of the higherenergy-density power needs of modern electronics and EVs.

Carbon-based anodes, such as (1) graphite intercalated with Li asdiscussed above, can demonstrate extended cycle lifespans due to thepresence of a surface-electrolyte interface layer (SEI), which resultsfrom the reaction between Li and surrounding electrolyte (or between Liand the anode surface/edge atoms or functional groups) during theinitial several charge-discharge cycles. Li ions consumed in thisreaction (referring to the formation of the SEI) may be derived fromsome of the Li ions originally intended for the charge transfer purpose(referring to the dissociation of elemental Li when intercalated withcarbon in a carbon-based structure, such as the anode, during Li ionmovement in electrolyte across a porous separator to the cathode asrelated to electron release and flow to power a load during Li ionbattery discharge cycles. As the SEI is formed, the Li ions become partof the inert SEI layer and become “irreversible”, in that they can nolonger be an active element (or ion) used for charge transfer. As aresult, it is desirable to minimize the amount of Li used for theformation of an effective SEI layer. In addition to SEI formation,Q_(ir), has been attributed to graphite exfoliation caused byelectrolyte/solvent co-intercalation and other side reactions.

Referring anode carbonaceous material introduced earlier, (2) amorphouscarbon, contains no (or very little) micro- or nano-crystallites.Amorphous carbon includes both so-called “soft carbon” and “hardcarbon”. Soft carbon refers to a carbon material that can be graphitizedat a temperature of about 2,500° C. or higher. In contrast, hard carbonrefers to a carbon material that cannot be graphitized at a temperaturehigher than 2,500° C.

However, in practice and industry, the so-called “amorphous carbons”commonly used as anode active materials may not be purely amorphous, butrather contain some minute amount of micro- or nano-crystallites, eachcrystallite being defined as a small number of graphene sheets (orientedas basal planes) that are stacked and bonded together by weak van derWaals forces. The number of graphene sheets can vary between one andseveral hundreds, giving rise to a c-directional dimension (thicknessL_(e)) of typically 0.34 nm to 100 nm. The length or width (L_(a)) ofthese crystallites is typically between tens of nanometers to microns.

Among this class of carbon materials, soft and hard carbons can beproduced by low-temperature pyrolysis (550-1,000° C.) and exhibit areversible specific capacity of 400-800 mAh/g in the 0-2.5 V range. Aso-called “house-of-cards” carbonaceous material has been produced withenhanced specific capacities approaching 700 mAh/g.

Research groups have obtained enhanced specific capacities of up to 700mAh/g by milling graphite, coke, or carbon fibers and have elucidatedthe origin of the additional specific capacity with the assumption thatin disordered carbon containing some dispersed graphene sheets (referredto as “house-of-cards” materials), Li ions are adsorbed on two sides ofa single graphene sheet. It has been also proposed that Li readily bondsto a proton-passivated carbon, resulting in a series of edge-orientedLi—C—H bonds. This provides an additional source of Li+in somedisordered carbons. Other research suggested the formation of Li metalmonolayers on the outer graphene sheets of graphite nano-crystallites.The discussed amorphous carbons were prepared by pyrolyzing epoxy resinsand may be more correctly referred to as polymeric carbons. Polymericcarbon-based anode materials have also been studied.

Chemistry, performance, cost and safety characteristics may vary acrossLi ion battery variants. Handheld electronics may use Li polymerbatteries (with a polymer gel as electrolyte) with Li cobalt oxide(LiCoO₂) as cathode material, which offers high energy density but maypresent safety risks, especially when damaged. Li iron phosphate(LiFePO₄), Li ion manganese oxide battery (LiMn₂O₄, Li₂MnO₃, or LMO),and Li nickel manganese cobalt oxide (LiNiMnCoO₂ or NMC) may offer lowerenergy density but provide longer useful lives and less likelihood offire or explosion. Such batteries are widely used for electric tools,medical equipment, and other roles. NMC in particular is oftenconsidered for automotive applications.

Electrical Conductance of Carbon-based Materials

Advances in high conductance carbon materials such as carbon nanotubes(CNT), graphene, amorphous carbon, and/or crystalline graphite inelectronics allows for the printing of these materials onto many typesof surfaces without necessarily using printed circuit boards, and/orwithout the use of materials or compounds that have been identified asbeing toxic to humans. Usage of high conductance carbon as a feedstockmaterial and/or other material during any one or more of the additivemanufacturing processes described above may facilitate the fabricationof batteries (including Li ion batteries) with micro-lattice structuressuitable for enhanced functionality, electric power storage anddelivery, and optimal efficiency. Moreover, although many of the devicesdescribed may serve as power sources (batteries, capacitors), those ofskill in the art will appreciate that such 3D printing technologies maybe reconfigured using high conductance carbon materials such as carbonnanotubes (CNT), graphene, amorphous carbon, or crystalline graphite canto form other electronic devices.

Printing technologies using high conductance carbon materials such ascarbon nanotubes (CNT), graphene, amorphous carbon, or crystallinegraphite may be implemented and/or otherwise incorporated in thefabrication of the following devices: antennas (tuned antennas), sensors(bio sensors), energy harvesters (photocells), and other electronicdevices.

Graphene

Graphene is an allotrope of carbon in the form of a single layer ofatoms in a two-dimensional hexagonal lattice in which one atom formseach vertex. It is the basic structural element of other allotropes,including graphite, charcoal, carbon nanotubes and fullerenes. It canalso be considered as an indefinitely large aromatic molecule, theultimate case of the family of flat polycyclic aromatic hydrocarbons.

Graphene has a special set of properties which set it apart from otherelements. In proportion to its thickness, it is about 100 times strongerthan the strongest steel. Yet its density is dramatically lower than anyother steel, with a surfacic (surface-related) mass of 0.763 mg persquare meter. It conducts heat and electricity very efficiently and isnearly transparent. Graphene also shows a large and nonlineardiamagnetism, even greater than graphite and can be levitated by Nd-Fe-Bmagnets. Researchers have identified the bipolar transistor effect,ballistic transport of charges and large quantum oscillations in thematerial. Its end-use application areas are widespread, finding uniqueimplementations in advanced materials and composites, as well as beingused as a formative material to construct ornate scaffolds usable in Liion battery electrodes to enhance ion transport and electric currentconduction to yield specific capacity and power delivery figures nototherwise attainable by conventional battery technologies.

Chemical Functionalization of Graphene

Functionalization, as generally understood and as referred to herein,implies the process of adding new functions, features, capabilities, orproperties to a material or substance by altering the surface chemistryof the material. Functionalization is a fundamental technique usedthroughout chemistry, materials science, biological engineering, textileengineering, and nanotechnology and may be performed by attachingmolecules or nanoparticles to the surface of a material, with a chemicalbond or through adsorption, the adhesion of atoms, ions or moleculesfrom a gas, liquid or dissolved solid to a surface to create a film ofthe adsorbate on the surface of the adsorbent without forming a covalentor ionic bond thereto.

Functionalization and dispersion of graphene sheets may be of criticalimportance to their respective end-use applications. Chemicalfunctionalization of graphene enables the material to be processed bysolvent-assisted techniques, such as layer-by-layer assembly,spin-coating, and filtration and also prevents the agglomeration ofsingle layer graphene (SLG) during reduction and maintains the inherentproperties of graphene.

Currently, the functionalization of graphene may be performed bycovalent and noncovalent modification techniques. In both instances,surface modification of graphene oxide followed by reduction has beencarried out to obtain functionalized graphene. It has been found thatboth the covalent and noncovalent modification techniques are veryeffective in the preparation of processable graphene.

However, electrical conductivity of functionalized graphene has beenobserved to decrease significantly compared to pure graphene. Moreover,the surface area of the functionalized graphene prepared by covalent andnon-covalent techniques decreases significantly due to the destructivechemical oxidation of flake graphite followed by sonication,functionalization and chemical reduction. To overcome these problems,studies have been reported on the preparation of functionalized graphenedirectly from graphite (one-step process). In all these cases, surfacemodification of graphene can prevent agglomeration and facilitates theformation of stable dispersions. Surface modified graphene can be usedfor the fabrication of polymer nanocomposites, Li ion batteryelectrodes, super-capacitor devices, drug delivery system, solar cells,memory devices, transistor device, biosensor, etc.

Graphite

Graphite, as commonly understood and as referred to herein, implies acrystalline form of elemental carbon with atoms arranged in a hexagonalstructure. Graphite occurs naturally in this form and is the most stableform of carbon under standard (atmospheric) conditions. Otherwise, underhigh pressures and temperatures, graphite converts to diamond. Graphiteis used in pencils and lubricants. Its high conductivity makes it usefulin electronic products such as electrodes, batteries, and solar panels.

Roll-to-Roll (R2R) Processing

R2R processing refers to the process of creating electronic devices on aroll of flexible plastic or metal foil. R2R processing may also refer toany process of applying coatings, printing, or performing otherprocesses starting with a roll of a flexible material and re-reelingafter the process to create an output roll. These processes, and otherssuch as sheeting, may be grouped together under the general term“converting”. When the rolls of material have been coated, laminated orprinted they can be subsequently cut and/or slit to their finished sizeon a slitter rewinder.

R2R processing of large-area electronic devices may reduce manufacturingcost. Other applications could arise which take advantage of theflexible nature of the substrates, such as electronics embedded intoclothing, 3D-printed Li ion batteries, large-area flexible displays, androll-up portable displays.

Oxidation-Reduction (Redox) Reactions

Redox are a type of chemical reaction in which the oxidation states ofatoms are changed. Redox reactions are characterized by the transfer ofelectrons between chemical species, most often with one species (thereducing agent) undergoing oxidation (losing electrons) while anotherspecies (the oxidizing agent) undergoes reduction (gains electrons). Thechemical species from which the electron is stripped is said to havebeen oxidized, while the chemical species to which the electron is addedis said to have been reduced.

Intercalation

As commonly understood and as referred to herein, in chemistry,intercalation is the reversible inclusion or insertion of a molecule (orion) into materials with layered structures. Examples are found ingraphite, graphene, and transition metal dichalcogenides.

Li Intercalation into Bi- or Multi-layer Graphene

Electrical storage capacity of graphene and the Li -storage process ingraphite currently present challenges requiring further development inthe field of Li ion batteries. Efforts have therefore been undertaken tofurther develop three-dimensional bi-layer graphene foam with fewdefects and a predominant Bernal stacking configuration, a type ofbilayer graphene where half of the atoms lie directly over the center ofa hexagon in the lower graphene sheet, and half of the atoms lie over anatom, and to investigate its Li -storage capacity, process, kinetics,and resistances. Li atoms may be stored only in the graphene interlayer.Further, various physiochemical characterizations of the staged Libilayer graphene products further reveal the regular Li -intercalationphenomena and illustrate this Li storage pattern of two-dimensions.

Electrochemical Capacitors (ECs)

Electrochemical capacitors (ECs), also referred to as “ultracapacitors”and/or “supercapacitors”, are considered for uses in hybrid or full EVs.ECs can supplement (or in certain uses replace) traditional batteries,including high-performance Li ion batteries, used in an EVs to provideshort bursts of power (forward propulsion) often needed for rapidacceleration. Traditional batteries may still be used provide uniformpower for cruising at normal highway speeds, but supercapacitors (withtheir ability to release energy much more quickly than batteries) mayactivate and supplement battery-provided power at times when the carneeds to accelerate, such as for merging, passing, emergency maneuvers,and hill climbing.

ECs must also store sufficient energy to provide an acceptable drivingrange, such as from 220-325 miles or more. And, to be cost- andweight-effective compared to additional battery capacity, ECs mustcombine adequate specific energy and specific power with long cyclelife, and meet cost targets as well. Specifically, ECs for applicationin EVs must store about 400 Wh of energy, be able to deliver about 40 kWof power for about 10 seconds, and provide high cycle-life (>100,000cycles).

The high volumetric capacitance density of an EC (10 to 100 timesgreater than conventional capacitors) derives from using porouselectrodes, which may incorporate, feature, and/or be constructed fromscaffolded graphene-based materials, to create a large effective “platearea” and from storing energy in the diffuse double layer. This doublelayer, created naturally at a solid-electrolyte interface when voltageis imposed, has a thickness of only about 1-2 nm, therefore forming anextremely small effective “plate separation.” In some ECs, stored energyis further augmented by pseudo-capacitance effects, occurring again atthe solid-electrolyte interface due to electrochemical phenomena such asthe redox charge transfer. The double layer capacitor is based on a highsurface area electrode material, such as activated carbon, immersed inan electrolyte. A polarized double layer is formed atelectrode-electrolyte interfaces providing high capacitance.

Overview Introduction

Advances in modern carbon-based materials(graphene) have enhancedapplications using such materials, such as in secondary batteries.Electrochemical Li intercalation or de-intercalation properties ofcarbon and carbon-based materials depend significantly on theirrespective morphology, crystallinity, orientation of crystallites, anddefects as well. Further, the electric storage capacity of a Li -ionbattery can be enhanced by the selection and integration of desirablenano-structured carbon materials such as carbon in certain allotropessuch as graphite and graphene, or nano-sized graphite, nanofibers,isolated single walled carbon nanotubes, nano-balls, and nano-sizedamorphous carbon, having small carbon nanostructures in which nodimension is greater than about 2 μm.

For example, known methods for fabricating carbon and Li -ion electrodesfor rechargeable Li cells include steps for forming a carbon electrodecomposed of graphitic carbon particles adhered by an ethylene propylenediene monomer binder used to achieve a carbon electrode capable ofsubsequent intercalation by Li-ions. The carbon electrode is reactedwith Li-ions to incorporate Li-ions into graphitic carbon particles ofthe electrode. An electrical current is repeatedly applied to the carbonelectrode to initially cause a surface reaction between the Li-ions andto the carbon and subsequently cause intercalation of the Li-ions intocrystalline layers of the graphitic carbon particles. With repeatedapplication of the electrical current, intercalation is achieved to neara theoretical maximum.

Other exfoliated graphite-based hybrid material compositions relate to:(a) micron- or nanometer-scaled particles or coating which are capableof absorbing and desorbing alkali or alkaline metal ions (particularly,Li ions); and, (b) exfoliated graphite flakes that are substantiallyinterconnected to form a porous, conductive graphite network comprisingpores. The particles or coating resides in a pore of the network or isattached to a flake of the network. The exfoliated graphite amount is inthe range of 5% to 90% by weight and the number of particles or amountof coating is in the range of 95% to 10% by weight.

Also, high capacity silicon-based anode active materials have been shownto be effective in combination with high capacity Li rich cathode activematerials. Supplemental Li is shown to improve the cycling performanceand reduce irreversible capacity loss for some silicon based activematerials. Silicon based active materials can be formed in compositeswith electrically conductive coatings, such as pyrolytic carbon coatingsor metal coatings, and composites can also be formed with otherelectrically conductive carbon components, such as carbon nano fibersand carbon nanoparticles.

And, known rechargeable batteries of an alkali metal having an organicelectrolyte experiences little capacity loss upon intercalation of thecarbonaceous electrode with the alkali metal. The carbonaceous electrodemay include a multi-phase composition including both highly graphitizedand less graphitized phases or may include a single phase, highlygraphitized composition subjected to intercalation of Li at above about50° C. Incorporation of an electrically conductive filamentary materialsuch as carbon black intimately interspersed with the carbonaceouscomposition minimizes capacity loss upon re-peated cycling.

Otherwise, a known Li based negative electrode material is characterizedby comprising 1 m²/g or more of carbonaceous negative electrode activematerial specific surface area, a styrene - butadiene rubber binder, anda fiber diameter formed to 1,000 nanometers of carbon fiber. Suchnegative electrode materials are used for Li batteries, which havedesirable characteristics, such as a low electrode resistance, highstrength of the electrode, an electrolytic solution having excellentpermeability, high energy density and a high rate charge/discharge. Thenegative electrode material contains 0.05 to 20 mass % of carbon fibersand a styrene at 0.1 to 6.0% by mass. Butadiene rubber forms the binderand may further contain 0.3 to 3% by mass thickener, such ascarboxymethyl methylcellulose.

Still further, existing technologies relate to a battery that has ananode active material that has been: (1) pre-lithiated; and, (2)pre-pulverized. This anode may be prepared with a method that comprises:(a) providing an anode active material; (b) intercalating or absorbing adesired amount of Li into the anode active material to produce apre-lithiated anode active material; (c) comminuting, referring to thereduction of solid materials from one average particle size to a smalleraverage particle size, by crushing, grinding, cutting, vibrating, orother processes, the pre-lithiated anode active material into fineparticles with an average size less than 10 μm (preferably <1 μand mostpreferably <200 nm); and, (d) combining multiple fine particles of thepre-lithiated anode active material with a conductive additive and/or abinder material to form the anode. The pre-lithiated particles areprotected by a Li ion-conducting matrix or coating material. The matrixmaterial is reinforced with nano graphene platelets.

Graphitic nanofibers have also been disclosed and include tubularfullerenes (commonly called “buckytubes”), nano tubes and fibrils, whichare functionalized by chemical substitution, are used as electrodes inelectrochemical capacitors. The graphitic nanofiber-based electrodeincreases the performance of the electrochemical capacitors. Preferrednanofibers have a surface area greater than about 200 m²/gm and aresubstantially free of micropores.

And, known high surface area carbon nanofibers have an outer surface onwhich a porous high surface area layer is formed. Methods of making thehigh surface area carbon nanofiber include pyrolizing a polymericcoating substance provided on the outer surface of the carbon nanofiberat a temperature below the temperature at which the polymeric coatingsubstance melts. The polymeric coating substance used as the highsurface area around the carbon nanofiber may include phenolics such asformaldehyde, polyacrylonitrile, styrene, divinyl benzene, cellulosicpolymers and cyclotrimerized diethynyl benzene. The high surface areapolymer which covers the carbon nanofiber may be functionalized with oneor more functional groups.

3D Self-Assembled Binder-less Mesoporous Carbon-based Particle

As presented above, conventional Li-intercalated carbon-basedcompositions or compounds may include traditional battery electrodematerials such as:

-   -   (1) graphene or multi-layer 3D graphene particles;    -   (2) electrically conductive carbon particles; and,    -   (3) binder, such as that provided as a fluid (for example,        liquid) form and/or in particulate form.

In conventional techniques, particles are all typically deposited, suchas being dropped into, existing slurry cast electrodes including currentcollectors made from metal foil such as copper. Slurry typically isprepared to contain an organic binder or binder material referred to asNMP, an organic compound consisting of a 5-membered lactam, used in thepetrochemical and plastics industries as a solvent, exploiting itsnonvolatility and ability to dissolve diverse materials. The ratio ofactive materials to conductive carbon or carbon-based particles isusually at 5 parts of conductive carbon to a predominant balance ofactive material with a nominal quantity of binder or binding material(such as NMP) included as well. The relative amounts of binder andconductive phases of carbon may be dictated by creating an electricallyconductive path or paths between larger particles of those mentioned.

Regarding difficulties related to binder implementation and usage insecondary batteries, studies have shown that developing high-performancebattery systems requires the optimization of every battery component,from electrodes and electrolyte to binder systems. However, theconventional strategy to fabricate battery electrodes by casting amixture of active materials, a nonconductive polymer binder, and aconductive additive onto a metal foil current collector usually leads toelectronic or ionic bottlenecks and poor contacts due to the randomlydistributed conductive phases. When high-capacity electrode materialsare employed, the high stress generated during electrochemical reactionsdisrupts the mechanical integrity of traditional binder systems,resulting in decreased cycle life of batteries. Thus, it is critical todesign novel binder systems, or scaffolded carbon-based electrodestructures that demonstrate structural integrity absent of usage of abinder, that can provide robust, low-resistance, and continuous internalpathways to connect all regions of the electrode.

In contrast to that traditionally done and further in view of addressingthe various shortcomings of binder performance related to decreasedcycle life of batteries as described above, presently disclosedinventive compositions of matter and methods or processes for theproduction thereof eliminate:

-   -   (1) any and all forms of a binder phase; and,    -   (2) potentially certain regions, features and/or aspects of a        conductive phase defined by larger carbon-based particles, such        as those including graphite, and/or forms of graphene extracted        or otherwise created from the exfoliation of graphite.

This is done by fabricating a particle where interconnected 3Dagglomerations of multiple layers of graphene sheets sinter (randomly,or with controlled directionality) or otherwise adjoin together to serveas a type of intrinsic, self-supporting, “binder” or joining materialthat serves as a binder replacement, effectively allowing for theelimination of a separate traditional binder material. Such a formatalso permits for the elimination of a current collector, which istypically a required component of many batteries. Elimination of thebinder phase and/or the current collector, as so disclosed by thepresent examples, provide for beneficial and desirable features, suchas:

-   -   (1) having low per-unit production cost allowing for        mass-producibility    -   (2) high reversible specific capacity    -   (3) low irreversible capacity    -   (4) small particle sizes (permitting for high throughput/rate        capacity)    -   (5) compatibility with commonly used electrolytes for convenient        integration and usage in commercial electrochemical cell        (battery) applications, and    -   (6) long charge-discharge cycle life for consumer benefit        (across any number of demanding end-use applications, including        automobiles, airplanes, and spacecraft).

Notably, techniques disclosed herein yield unexpected favorable resultsby, instead of relying upon traditional processes to create graphenesheets such as from the exfoliation of graphite, synthesizing amulti-modal mesoporous carbon-based particle in an atmosphericplasma-based vapor flow stream either in-flight (to nucleate from aninitially formed carbon-based homogenous nucleation) or depositeddirectly onto a supporting or sacrificial substrate. Therefore,techniques permit for the growth of ornate carbon-based structuresindependent (absent) of a traditionally required seed particle (uponwhich nucleation occurs).

In conventional techniques, the production of functional graphene reliesupon usage of graphite as a starting material. Graphite, being aconductive material, has been used as an electrode in batteries andother electrochemical devices. In addition to its function as an inertelectrode, electrochemical methods have been employed to form graphiteintercalation compounds (GICs) and, more recently, to exfoliate graphiteinto few-layered graphene (“exfoliation”, as generally understood and asreferred to herein, implies—in an intercalation chemistry relatedcontext—the complete separation of layers of material, and typicallyrequires aggressive conditions involving highly polar solvents andaggressive reagents). Electrochemical methods are attractive as theyeliminate the use of chemical oxidants as the driving force forintercalation or exfoliation, and an electromotive force is controllablefor tunable GICs. More importantly, the extensive capabilities ofelectrochemical functionalization and modification enable the facilesynthesis of functional graphene and its value-added nanohybrids.

Unlike exfoliation, or the thermal exfoliation of graphite to producegraphene, the presently disclosed methods relate to one or morecarbon-inclusive gaseous species, such as those including methane (CH₄),being flowed into a reaction chamber of a microwave-based or thermalreactor. Upon receipt of energy (such as electromagnetic radiationand/or thermal energy), incoming gaseous species spontaneously crack toform allotropes with other cracked carbons (from additional gaseousspecies supplied into the reactor) to create an initial carbon-basedsite (such as a formed particle), which either has (or otherwisefacilitates):

-   -   a. additional particles that grow or nucleate off of defects        from that initial formed particle; or,    -   b. sinter additional carbon-based particles, where there is        sufficient local energy at the collision spot for the colliding        particles to sinter together (to be described in further detail        below).

Systen Structure 3D Self-Assembled Binder-Less Multi-Modal MesoporousCarbon-Based Particle—In Detail

FIG. 1A shows a three-dimensional (3D) self-assembled binder-lessmulti-modal mesoporous carbon-based particle 100A having controllableelectrical and ionic conducting gradients distributed throughout, withinwhich various aspects of the subject matter disclosed herein may beimplemented. A mesoporous material, as generally understood and asreferred to herein, implies a material containing pores with diametersbetween 2 and 50 nm, according to IUPAC nomenclature For the purposes ofcomparison, IUPAC defines microporous material as a material havingpores smaller than 2 nm in diameter and macroporous material as amaterial having pores larger than 50 nm in diameter.

Mesoporous materials may include various types of silica and aluminathat have similarly sized mesopores. Mesoporous oxides of niobium,tantalum, titanium, zirconium, cerium and tin have been researched andreported. Of all the variants of mesoporous materials, mesoporous carbonhas achieved particular prominence, having direct applications in energystorage devices. Mesoporous carbon is defined as having porosity withinthe mesopore range, and this significantly increases the specificsurface area. Another common mesoporous material is “activated carbon”,referring to a form of carbon processed to have small, low-volume poresthat increase the surface area. Activated carbon, in a mesoporouscontext, is typically composed of a carbon framework with bothmesoporosity and microporosity (depending on the conditions under whichit was synthesized). According to IUPAC, a mesoporous material can bedisordered or ordered in a mesostructure. In crystalline inorganicmaterials, mesoporous structure noticeably limits the number of latticeunits, and this significantly changes the solid-state chemistry. Forexample, the battery performance of mesoporous electroactive materialsis significantly different from that of their bulk structure.

Mesoporous carbon-based particle 100A is nucleated and grown in anatmospheric plasma-based vapor flow stream of reagent gaseous species,which may include methane (CH₄), to form an initial carbon-containingand/or carbon-based particle. That initial particle may be expanded uponeither:

-   -   (1) “in-flight”, describing the systematic coalescence        (referring to nucleation and/or growth from an initial        carbon-based homogenous nucleation independent of a seed        particle) of additional carbon-based material derived from        incoming carbon-containing gas mid-air within a microwave-plasma        reaction chamber (as shown by micrograph 100D in FIG. 1D); or,    -   (2) grown (and/or deposited) directly onto a supporting or        sacrificial substrate, such as a current collector, within a        thermal reactor.        In chemistry-related context, “coalescence” implies a process in        which two phase domains of the same composition come together        and form a larger phase domain. Alternatively put, the process        by which two or more separate masses of miscible substances seem        to “pull” each other together should they make the slightest        contact. Mesoporous carbon-based particle 100A, may be        alternatively referred to as just “particle”, and/or by any        other similar term. The term “mesoporous”, as both generally        understood and as used herein, may be defined as a material        containing pores with diameters between 2 and 50 nm, according        to International Union of Pure and Applied Chemistry (“IUPAC”)        nomenclature.

Referring to synthesis and/or growth of mesoporous carbon-based particle100A within a reaction chamber in and/or otherwise associated with amicrowave-based reactor, such as a reactor disclosed by Stowell, et al.,“Microwave Chemical Processing Reactor”, U.S. Pat. No. 9,767,992, (Sep.19, 2017), incorporated by reference herein in its entirety, or thermalreactor, referring generally to a chemical reactor defined by anenclosed volume in which a temperature-dependent chemical reactoroccurs.

Mesoporous carbon-based particle 100A (also mesoporous carbon-basedparticle 100E as shown in FIG. 1E) is synthesized with athree-dimensional (3D) hierarchical structure comprising short range,local nano-structuring in combination with long range approximatefractal feature structuring, which in this context refers to theformation of successive layers involving the 90-degree rotation of eachsuccessive layer relative to the one beneath it, and so on and so forth,allowing for the creation of vertical (or substantially vertical) layersand/or intermediate (“inter”) layers.

The plurality of hierarchical (and/or contiguous) pores 107F (as shownin FIG. 1F) at least in part further define open porous scaffold 102Awith one or more Li ion diffusion pathways 109F (as shown in FIG. 1F)having:

-   -   (1) microporous frameworks defined by a dimension 101F of >50 nm        that provide tunable Li ion conduits;    -   (2) mesoporous channels defined by a dimension 101F of about 20        nm to about 50 nm (generally defined under IUPAC nomenclature        and referred to as “mesopores” or “mesoporous”) that act as Li        ion-highways for rapid Li ion transport therein; and    -   (3) microporous textures defined by a dimension 103F of <4 nm        for charge accommodation and/or active material confinement.

Li ion diffusion pathways 109F and/or hierarchical porous network 100Fmore generally may act as or otherwise provide active Li intercalatingstructures, which may provide a source for specific capacity of an anodeor cathode Li ion battery electrode at between about 744 mAh/g to about1,116 mAh/g. Li may infiltrate open porous scaffold to at leastpartially chemically react with exposed carbon therein. Mesoporouscarbon-based particle 100A may be synthesized at least in part by avapor flow stream of gaseous reagents including any one or more of asaturated or unsaturated hydrocarbon, such as methane (CH₄), flowed ontoa substrate in a reactor, such as a microwave-based reactor and/or athermal reactor.

One or more physical, electrical, chemical and/or material properties ofthe mesoporous carbon-based particle 100A may be defined during itssynthesis. Also, dopants (referring to traces of impurity element thatis introduced into a chemical material to alter its original electricalor optical properties, such as Si, SiO, SiO2, Ti, TiO, Sn, Zn, and/orthe like) may be dynamically incorporated during synthesis of mesoporouscarbon-based particle 100A to at least in part affect materialproperties including: electrical conductivity, wettability, and/or ionconduction or transport through hierarchical porous network 100F.Microporous textures having dimension 103F and/or hierarchical porousnetwork 100F more generally may be synthesized, prepared or otherwisecreated to also (or otherwise) include smaller pores for chemicalmicro-confinement, the smaller pores being defined as ranging from 1 to3 nm. Also, each graphene sheet (as shown in FIG. 1C) may range from 50to 200 nm in diameter (L_(a)).

Hierarchical porous network 100F, may be a further magnified and/ordetailed variant of open porous scaffold 102A, may provide one or moreactive Li intercalating structures, to be further described in structureand/or functionality in connection with FIGS. 6-19C, which show varioustopic diagrams, flowcharts, schematics, photographs and/or micrographsrelated to lithium, lithium ion, sulfide, and/or lithium, sulfur and/orother element derived chemical substances and/or compounds infiltratedand/or infused into the multi-layered carbon-based scaffolded structureshown in FIG. 4B. Open porous scaffold 102A may be created independentof a binder, such as a traditional, nonconductive polymer bindertypically used in conjunction with and a conductive additive onto ametal foil current collector in battery end-use applications.Traditional configurations involving usage of a binder can lead toelectronic/current conduction-related or ionic constrictions and poorcontacts due to randomly distributed conductive phases. Moreover, whenhigh-capacity electrode materials are employed, relatively high physicalstress generated during electrochemical reactions can disrupt mechanicalintegrity of traditional binder systems, therefore, in turn, reducingcycle life of batteries.

A vapor flow stream used to synthesize mesoporous carbon-based particle100A may be at least flowed in part into a vicinity of a plasma, such asthat generated and/or flowed into a reactor and/or chemical reactionvessel. Such a plasma reactor may be configured to propagate microwaveenergy toward the vapor flow stream to at least in part assist withsynthesis of mesoporous carbon-based particle 100A, may involvecarbon-particle based and/or derived nucleation and growth fromconstituent carbon-based gaseous species, such as methane (CH₄), wheresuch nucleation and growth may substantially occur from an initiallyformed carbon-based homogenous nucleation independent of a seed particlewithin a reactor. More particularly, such a reactor accommodates controlof gas-solid reactions under non-equilibrium conditions, where thegas-solid reactions may be controlled at least in part by any one ormore of:

-   -   (1) ionization potentials and/or thermal energy associated with        constituent carbon-based gaseous species introduced to the        reactor for synthesis of the mesoporous carbon-based particle;        and/or    -   (2) kinetic momentum associated with the gas-solid reactions.

The vapor flow stream may be flowed into a reactor and/or reactionchamber for the synthesis of mesoporous carbon-based particle 100A atsubstantially atmospheric pressure. And, change in wettability ofmesoporous carbon-based particle 100A (and/or any constituent memberssuch as open porous scaffold 102A) at least in part may involveadjustment of polarity of a carbon matrix associated with mesoporouscarbon-based particle 100A.

Those skilled in the art will appreciate that the representationsprovided in FIGS. 1A-1D, lE and 1F, are provided as examples. Samplerepresentations are shown of mesoporous carbon-based particle 100A,including:

-   -   (1) when synthesized in a microwave-based reactor in micrograph        100D in FIG. 1D;    -   (2) when synthesized in the form of multi-shell fullerene (CNO)        shown in micrograph 100H in FIG. 1H;    -   (3) when used to decorate graphite to form graphene-decorated        graphite shown in micrograph 1001 in FIG. 11; and,    -   (4) when synthesized in-flight in a microwave reactor as shown        by micrograph 100J in FIG. 1J.

Mesoporous Carbon-Based Particle-13 Procedures for Synthesis MicrowaveReactor

As introduced above, a vapor flow stream including carbon-containingconstituent species, such as methane (CH₄) may be flowed into one of twogeneral reactor types:

-   -   (1) a thermal reactor; or,    -   (2) a microwave-based (and/or “microwave”) reactor. Suitable        types of microwave reactors are disclosed by Stowell, et al.,        “Microwave Chemical Processing Reactor”, U.S. Pat. No. 9,767,992        (Sep. 19, 2017), incorporated herein by reference in its        entirety.

An example microwave processing reactor used to synthesize mesoporouscarbon-based particle 100A may include microwave-generating energysource and a field-enhancing waveguide. The field-enhancing waveguidehas a field-enhancing zone between a first cross-sectional area and asecond cross-sectional area of the waveguide, and also has a plasma zoneand a reaction zone. The second cross-sectional area is smaller than thefirst cross-sectional area, is farther away from the microwave energysource than the first cross-sectional area and extends along a reactionlength of the field-enhancing waveguide. The supply gas inlet isupstream of the reaction zone. In the reaction zone, a majority of thesupply gas flow is parallel to the direction of the microwave energypropagation. The supply gas is used to generate a plasma in the plasmazone to convert a process input material into separated components inthe reaction zone at a pressure of at least 0.1 atmosphere, with apreference for 1 atmosphere where the surprising favorable physicalproperties of mesoporous carbon-based particle 100A, as discussed above,were discovered.

Propagation of microwave energy toward the carbon-containing orcarbon-based vapor flow stream at least in part assists with synthesisof mesoporous carbon-based particle 100Aand facilitates carbon-particlenucleation and growth within a reactor.

The term “in-flight” implies a novel method of chemical synthesis basedon contacting particulate material derived from inflowingcarbon-containing gaseous species, such as those containing methane(CH₄), to “crack” such gaseous species. “Cracking”, as generallyunderstood and as referred to herein, implies the technical process ofmethane pyrolysis to yield elemental carbon (such as high-quality carbonblack) and hydrogen gas, “without the problematic contamination bycarbon monoxide, and . . . with virtually no carbon dioxide emissions.”A basic endothermic reaction that may occur within a microwave reactoris shown as equation (1) below:

CH₄+74.85 kJ/mol→C+2H2   (1)

Carbon derived from the above-described “cracking” process and/or asimilar or a dissimilar process may fuse together while being dispersedin a gaseous phase, referred to as “in-flight”, to create carbon-basedparticles, structures, (substantially) 2D graphene sheets, 3Dagglomerations, and/or pathways defined therein, including :

-   -   (1) a plurality of interconnected 3D agglomerations 101B of        multiple layers of graphene sheets 101C (also, each sheet of        graphene is schematically depicted in FIG. 1C) that are sintered        together to form an open porous scaffold 102A that facilitates        electrical conduction along and across contact points of the        graphene sheets 101C (which, as shown in FIG. 1B, may include        and/or refer to 5 to 15 layers of graphene are oriented in a        stacked configuration to have a vertical height referred to as a        stack height (L_(c))); and,    -   (2) a plurality of hierarchical pores 107F (as shown in FIG. 1F,        and including pores 104F, 105F, and/or pathways 106F and/or        109F, any one or more which may be of a different dimension than        the others) interspersed with the plurality of interconnected 3D        agglomerations 101B of multiple layers of graphene sheets 101C,        that may comprise one or more of single layer graphene (SLG),        few layer graphene (FLG) defined as ranging from 5 to 15 layers        of graphene, or many layer graphene (MLG), throughout the        multi-modal mesoporous carbon-based particle 100A and/or 100E to        define a hierarchical porous network 100F that facilitates rapid        Li ion (Li+) 108F diffusion therein by orienting and/or        manipulating, such as by shortening, Li ion diffusion pathways        106F and/or 109F.

As introduced earlier, interconnected 3D agglomerations of multiplelayers of graphene sheets 101B sinter (or otherwise adjoin) together toserve as a type of intrinsic, self-supporting, “binder” or joiningmaterial allowing for the elimination of a separate traditional bindermaterial. Sintering, or “frittage”, as commonly understood and asreferred to herein, implies the process of compacting and forming asolid mass of material by heat or pressure without melting it to thepoint of liquefaction. Sintering happens naturally in mineral depositsor as a manufacturing process used with metals, ceramics, plastics, andother materials. The atoms in the materials diffuse across theboundaries of the particles, fusing the particles together and creatingone solid piece. Since sintering temperature does not have to reach themelting point of the material, sintering is often chosen as the shapingprocess for materials with extremely high melting points such astungsten (W) and molybdenum (Mo). The study of sintering in metallurgypowder-related processes is known as powder metallurgy. An example ofsintering can be observed when ice cubes in a glass of water adhere toeach other, which is driven by the temperature difference between thewater and the ice. Examples of pressure-driven sintering are thecompacting of snowfall to a glacier, or the forming of a hard snowballby pressing loose snow together.

Few layer graphene (FLG), defined herein as ranging from 5 to 15 layersor sheets of graphene, are sintered, substantially as so-describedabove, at an angle that is not flat relative to other FLG sheets tonucleate and/or grow at an angle and therefore “self-assemble” overtime. Moreover, process conditions may be tuned to achieve synthesis,nucleation, and/or growth of 3D multi-modal mesoporous carbon-basedparticles on a component and/or a wall surface within a reactionchamber, or entirely in-flight (upon contact with other carbon-basedmaterials).

Electrical conductivity of deposited carbon and/or carbon-basedmaterials may be tuned by adding metal additions into the carbon phasein the first part of the deposition phase or to vary the ratios of thevarious particles discussed. Other parameters and/or additions may beadjusted, as a part of an energetic deposition process, such that thedegree of energy of deposited carbon and/or carbon-based particles willeither: (1) bind together; or, (2) not bind together.

By nucleating and/or growing the multi-modal mesoporous carbon-basedparticle in an atmospheric plasma-based vapor flow stream eitherin-flight or directly onto a supporting or sacrificial substrate, anumber of the steps and components found in both traditional batteriesand traditional battery-making processes may be eliminated. Also, aconsiderable amount of tailoring and tunability can be enabled orotherwise added into the discussed carbons and/or carbon-basedmaterials.

For instance, a traditional battery may use a starting stock of activematerials, graphite, etc., which may be obtained as off-the-shelfmaterials to be mixed into a slurry. In contrast, the 3D self-assembledbinder-less multi-modal mesoporous carbon-based particle 100A disclosedherein may enable, as a part of the carbon or carbon-based materialsynthesis and/or deposition process, tailoring and/or tuning theproperties of materials, in real-time, as they are being synthesizedin-flight and/or deposited onto a substrate. This capability presents asurprising, unexpected and substantial favorable departure from thatcurrently available regarding creation of carbon-based scaffoldedelectrode materials in the secondary battery field.

Reactor and/or reactor design of that disclosed by Stowell, et al.,“Microwave Chemical Processing Reactor”, U.S. Pat. No. 9,767,992 (Sep.19, 2017) may be adjusted, configured and/or tailored to control wantedor unwanted nucleation sites on internal surfaces of reaction chambersexposed to carbon-based gaseous feedstock species (such as methane(CH₄)). In-flight particles qualities may be influenced by theirsolubility in the gaseous species in which they are flowed in such thatonce a certain energy level is achieved, it is not inconceivable forcarbon to “crack off” (as so described by “cracking”) and form its ownsolid in a microwave reactor.

Adjusting for Unwanted Carbon Accumulation on Reaction Chamber Walls

Moreover, tuning of disclosed reactors and related systems may beperformed to both proactively and reactively address issues associatedwith carbon-based microwave reactor clogging. For instance, opensurfaces, feed holes, hoses, piping and/or the like may accumulateunwanted carbon-based particulate matter as a by-product of syntheticprocedures performed to create mesoporous carbon-based particle 100A. Acentral issue observed in a microwave reactor may include this tendencyto experience clogging in and/or along orifices, the reason beingrelated to walls and other surfaces exposed to in-flowing gaseouscarbon-containing species having carbon solubility as well. Therefore,is it possible to unwantedly grow on the walls of a reaction chamberand/or on the exit tube. Over time, those growths will extend out andultimately impinge flow and can shut down chemical reactions occurringwithin the reactor and/or reaction chamber. Such a phenomena may be akinto tube (exhaust) wall build-up of burnt oil in a high-performance orracing internal combustion engine, where, instead of burning(combusting) fossil-fuel based gasoline, methane is used to result inthe unwanted deposit of carbon on reaction chamber wells since metalinside the reaction chamber itself has a carbon solubility level.

Although methane is primarily used to create mesoporous carbon-basedparticle 100A, in theory any carbon-containing and/or hydrocarbon gas,like C₂ or acetylene or any one or more of: C₂H₂, CH₄, butane, naturalgas, biogas (derived from decomposition of biological matter) willfunction to provide a carbon-containing source.

The described uncontrolled and unwanted carbon growth within exposedsurfaces of a microwave reactor may be compared to that occurring withinan internal combustion engine exhaust manifold (rather than within acylinder bore) of the engine, especially where the plume of plasma(and/or hot, excited gas about to enter into the plasma phase) is at theonset of the manifold, and burnt gas and carbon-based fragments aretraveling down and plugging-up flow through the manifold, cross-pipes,and catalytic converter, and exit-pipes. Process conditions maytherefore be proactively tuned to adjust and therefore accommodate forpotential carbon-build-up as so-described in the microwave reactor,which (as disclosed and referred to) relies on the presence of a plasmafor hydrocarbon gas cracking. To maintain this plasma, a certain set ofconditions must be maintained, otherwise back-pressure accumulation canpotentially destroy the plasma prior to its creation and subsequentignition, etc.

Thermal Reactor

In the alternative (or in certain cases, in addition or combinationwith) synthesis of mesoporous carbon-based particle 100A in amicrowave-based and/or microwave reactor as substantially describedabove, specifically structured and/or scaffolded carbons and/orcarbon-based structures can be created by “cracking” hydrocarbons purelyby heat application in a reactor featuring application of thermalradiation (heat), referred to herein as a “thermal reactor”. Exampleconfigurations may include exposure of incoming carbon-based gaseousspecies (such as any one or more of the aforementioned hydrocarbons) toa heating element (similar to a wire in a lightbulb).

The heating element heats up the inside of a reaction chamber whereincoming carbon-containing gas is ionized. The carbon-containing gas isnot burnt, due to the absence of sufficient oxygen to sustaincombustion, but is rather ionized from contact with incoming thermalradiation (heat) and/or other forms of thermal energy to causenucleation of constituent members of mesoporous carbon-based particle100A, and ultimately synthesize, via nucleation, mesoporous carbon-basedparticle 100A in its entirety. In thermal reactors, some, or most, ofthe observed nucleation of carbon-based particles can occur on walls oron the heating element itself. Nevertheless, particles can stillnucleate which are small enough to be cracked by the speed of flowinggas, such particles are captured to assist in the creation of mesoporouscarbon-based particle 100A.

Cracked carbons can be used to create CNO as shown, for example, by 100Hin FIG. 1H, and/or fullerenes, and smaller fractions of carbons withfullerene internal crystallography.

In comparing synthesis of mesoporous carbon-based particle 100A via thetwo discussed pieces of equipment, microwave and thermal reactors, thefollowing distinctions have been observed:

-   -   (1) microwave reactors can provide tuning capabilities suitable        to provide a broader range of allotropes of carbon; whereas,    -   (2) thermal reactors tend to allow for the fine-tuning of        process parameters, such as heat flow, temperature, and/or the        like, to achieve the needs of specific end-use application        targets of mesoporous carbon-based particle 100A.

For instance, thermal reactors are currently being used to build Li Selectrochemical cell electrodes, such as anodes and cathodes. Typicaltreatment process temperatures range in the thousands of Kelvin, withoptimal, surprising, and otherwise unexpected favorable performanceproperties, such as referring to mesoporous carbon-based particle 100Aand/or carbon-based aggregates associated therewith, when compressed,have an electrical conductivity greater than 500 S/m, or greater than5000 S/m, or from 500 S/m to 20,000 S/m. Optimal performance has beenobserved at between 2,000-4,000 K.

Mesoporous Carbon-Based Particle—Physical Properties & Implementation inLi Ion and Li S Batteries

Any one or more of the carbon-based structures, intermediaries, orfeatures associated with mesoporous carbon-based particle 100A may beincorporated at least in part into a secondary battery electrode, suchas that of a lithium ion battery, as substantially set forth by Lanning,et al., “Lithium Ion Battery and Battery Materials”, U.S. Pat. Pub. No.2019/0173125, (published on Jun. 6, 2019), incorporated by referenceherein in its entirety.

Particulate carbon contained in and/or otherwise associated withmesoporous carbon-based particle 100A may be implemented in a Li ionbattery cathode as a structural and/or electrically conductive materialand have at least a substantially a mesoporous structure as shown byhierarchical porous network 100F with a wide distribution of pore sizes(also referred to as a multi-modal pore size distribution). For example,mesoporous particulate carbon can contain multi-modal distribution ofpores in addition or in the alternative to plurality of hierarchicalpores 107F (as shown in FIG. 1F) that at least in part further defineopen porous scaffold 102A with one or more Li ion diffusion pathways109F. Such pores may have sizes from 0.1 nm to 10 nm, from 10 nm to 100nm, from 100 nm to 1 micron, and/or larger than 1 micron. Porestructures can contain pores with a bi-modal distribution of sizes,including smaller pores (with sizes from 1 nm to 4 nm) and larger pores(with sizes from 30 to 50 nm). Such a bimodal distribution of pore sizesin mesoporous carbon-based particle 100A can be beneficial insulfur-containing cathodes in lithium ion batteries, as the smallerpores (1 to 4 nm in size) can confine the sulfur (and in some casescontrol of saturation and crystallinity of sulfur and/or of generatedsulfur compounds) in the cathode, and the larger pores (30 to 50 nm insize, or pores greater than twice the size of solvated lithium ions) canenable and/or facilitate rapid diffusion (or, mass transfer) of solvatedLi ions in the cathode.

As introduced earlier, the lithium-sulfur battery (Li—S battery) is atype of rechargeable battery, notable for its high specific energy. Alithium/sulfur (Li/S) battery (such as that represented by sulfur (S)infiltrated into hierarchical pores 107F of mesoporous particle 100E(such as where S infiltrates open porous scaffold 102A to deposit oninternal surfaces of mesoporous carbon-based particle 100A, 100E and/orwithin pores 107F), as shown in FIGS. 1F and lE respectively, and byschematic 100G shown in FIG. 1G, showing intermediate steps associatedwith the reduction of sulfur to the sulfide ion (S²⁻)). Incorporation ofS into Li ion batteries may result in a 3-5 fold higher theoreticalenergy density than state-of-art Li ion batteries without S, andresearch has been ongoing for more than three decades. However, thecommercialization of Li/S battery still, in some respects, cannot befully realized due to many problematic issues, including short cyclelife, low cycling efficiency, poor safety and a high self-dischargerate. All these issues are related to the dissolution of lithiumpolysulfide (PS), the series of sulfur reduction intermediates, inliquid electrolyte and to resulting parasitic reactions with the lithiumanode and electrolyte components. On the other hand, the dissolution ofPS is essential for the performance of a Li/S cell. Without dissolutionof PS, the Li/S cell cannot operate progressively due to thenon-conductive nature of elemental sulfur and its reduction products.

Mesoporous Carbon-Based Particle—Formed to Address Polysulfide(PS)-Related Challenges

Seeking to address at least some of the challenges associated with suchpolysulfide (PS) systems, mesoporous carbon-based particle 100A andcathodic active material form a meta-particle framework, where cathodicelectroactive materials (such as elemental sulfur that may form PScompounds 100G as shown in FIG. 1G) are arranged within mesoporouscarbon pores/channels, such as within any one or more of hierarchicalpores 107F (as shown in FIG. 1F, including pores 104F, 105F, and/orpathways 106F and/or 109F). S can be, for example, substantiallyincorporated within pores 107F at a loading level that represents35-100% of the total weight/volume of active material in mesoporouscarbon-based particle 100A and/or 100E overall.

This type of organized particle framework can provide a low resistanceelectrical contact between the insulating cathodic electroactivematerials (such as elemental sulfur) and the current collector whileproviding relatively high exposed surface area structures that arebeneficial to overall specific capacity (and that may be at least assistlithium ion micro-confinement as enhanced by the formation of Li Scompounds temporarily retained in hierarchical pores 107F, and thecontrolled release and migration of Li ions as related to electriccurrent conduction) in a battery electrode and/or system.Implementations of mesoporous carbon-based particle 100A can alsobenefit cathode stability by trapping at least some portion of anycreated polysulfides by using tailored structures, such as that shown byhierarchical pores 107F, to actively prevent them from unwantedlymigrating through electrolyte to the anode resulting in unwantedparasitic chemical reactions associated with battery self-discharge.

Unwanted Migration of Polysulfides during Li S Battery SystemUsage—Generally

With reference to polysulfide shuttle mechanisms observed in Li Sbattery electrodes and/or systems, polysulfides dissolve very well inelectrolytes. This causes another lithium-sulfur cell characteristic,the so-called shuttle mechanism. The polysulfides S_(n2)—that form anddissolve at the cathode, diffuse to the lithium anode and are reduced toLi₂S₂ and Li₂S. (The polysulfide species S_(n)2—that form at the cathodeduring discharging dissolve in the electrolyte there. A concentrationgradient versus the anode develops, which causes the polysulfides todiffuse toward the anode. Step by step, the polysulfides are distributedin the electrolyte.) Subsequent high-order polysulfide species reactwith these compounds and form low-order polysulfides S_((n-x)). Thismeans that the desired chemical reaction of sulfur at the cathode partlyalso takes place at the anode in an uncontrolled fashion (chemical orelectrochemical reactions are conceivable), which negatively influencescell characteristics.

If low-order polysulfide species form near the anode, they diffuse tothe cathode. When the cell is discharged, these diffused species arefurther reduced to Li₂S₂ or Li₂S. Simply put, the cathode reactionpartly takes place at the anode during the discharging process or,rather, the cell self-discharges. Both are undesirable effectsdecreasing [specific] capacity. In contrast to that, the diffusion tothe cathode during the charging process is followed by a re-oxidation ofthe polysulfide species from low order to high order. These polysulfidesthen diffuse to the anode again. This cycle is generally known as theshuttle mechanism. If the shuttle mechanism is very pronounced, it ispossible that a cell can accept an unlimited charge, it is ‘chemicallyshort-circuited’.

In general, the shuttle mechanism causes a parasitic sulfur activematter loss. This is due to the uncontrolled separation of Li₂S₂ andLi₂S outside of the cathode area and it eventually causes a considerabledecrease in cell cycling capability and service life. Further agingmechanisms can be an inhomogeneous separation of Li₂S₂ and Li₂S on thecathode or a mechanical cathode structure breakup due to volume changesduring cell reaction.

Hierarchical Pores of Mesoporous Carbon-Based Particle formed to PreventLithium Shuttle (referring to Loss) to the Anode

To address the unwanted phenomenon of PS shuttling as so describedabove, any one or more of the plurality of hierarchical pores 107F ofmesoporous carbon-based particle 100A in a cathode can provide asuitable region, formed with an appropriate dimension, to drive thecreation of lower order polysulfides (such as S and Li₂S) and thereforeprevent the formation of the higher order soluble polysulfides(Li_(x)S_(y) with y greater than 3) that facilitate lithium shuttle(i.e., loss) to the anode. As described herein, the structure of theparticulate carbon and the cathode mixture of materials can be tunedduring particulate carbon formation (within a microwave plasma orthermal reactor). In addition, cathodic electroactive materials(elemental sulfur) solubility and crystallinity in relation to lithiumphase formation, can be confined/trapped within the micro/meso porousframework.

The present lithium ion batteries can incorporate particulate carbon aspresented by mesoporous carbon-based particle 100A and/or anyderivatives thereof into the cathode, anode, and/or one or bothsubstrates with improved properties compared to conventional carbonmaterials. For example, the particulate carbon can have highcompositional purity, high electrical conductivity, and a high surfacearea compared to conventional carbon materials. In some embodiments, theparticulate carbon also has a structure that is beneficial for batteryproperties, such as small pore sizes and/or a mesoporous structure. Insome cases, a mesoporous structure can be characterized by a structurewith a wide distribution of pore sizes (with a multimodal distributionof pore sizes). For example, a multimodal distribution of pore sizes canbe indicative of structures with high surface areas and a large quantityof small pores that are efficiently connected to the substrate and/orcurrent collector via material in the structure with larger featuresizes (i.e., that provide more conductive pathways through thestructure). Some non-limiting examples of such structures are fractalstructures, dendritic structures, branching structures, and aggregatestructures with different sized interconnected channels (composed ofpores and/or particles that are roughly cylindrical and/or spherical).

In some embodiments, the substrate, cathode, and/or anode contains oneor more particulate carbon materials. In some embodiments, theparticulate carbon materials used in the lithium ion batteries describedherein are described in U.S. Pat. No. 9,997,334, entitled “SeedlessParticles with Carbon Allotropes,” which is assigned to the sameassignee as the present application, and is incorporated herein byreference as if fully set forth herein for all purposes. In someembodiments, the particulate carbon materials contain graphene-basedcarbon materials that comprise a plurality of carbon aggregates, eachcarbon aggregate having a plurality of carbon nanoparticles, each carbonnanoparticle including graphene, optionally including multi-walledspherical fullerenes, and optionally with no seed particles (such aswith no nucleation particle). In some cases, the particulate carbonmaterials are also produced without using a catalyst. The graphene inthe graphene-based carbon material has up to 15 layers. A ratio (i.e.,percentage) of carbon to other elements, except hydrogen, in the carbonaggregates is greater than 99%. A median size of the carbon aggregatesis from 1 micron to 50 microns, or from 0.1 microns to 50 microns. Asurface area of the carbon aggregates is at least 10 m²/g, or is atleast 50 m²/g, or is from 10 m²/g to 300 m²/g or is from 50 m²/g to 300m²/g, when measured using a Brunauer-Emmett-Teller (BET) method withnitrogen as the adsorbate. The carbon aggregates, when compressed, havean electrical conductivity greater than 500 S/m, or greater than 5000S/m, or from 500 S/m to 20,000 S/m.

Mesoporous Carbon-Based Particle—Departure from Conventional Technologyto Yield Surprising Favorable Results

Conventional composite-type Li-ion or Li S battery electrodes (shown inFIG. 2B) may be fabricated from a slurry cast mixture of activematerials (shown as in FIG. 2A), including: conductive additives (suchas fine carbon black and graphite for usage in a battery cathode at aspecific aspect ratio), and polymer-based binders that are optimized tocreate a unique self-assembled morphology defined by an interconnectedpercolated conductive network. While, in conventional preparations orapplications, additives and binders can be optimized to improveelectrical conductivity there-through (by, for example, offering lowerinterfacial impedance) and therefore correspondingly yield improvementsin power performance (delivery), they represent a parasitic mass thatalso necessarily reduces specific (also referred to as gravimetric)energy and density, an unwanted end result for today's demandinghigh-performance battery applications.

To minimize losses due to parasite mass (such as that caused byincreased active and/or inactive ratio), and concurrently enable fasteraccess of electrolyte to the complete surface of an electrode,orienting, re-orienting, and/or otherwise organizing or repositioningion diffusion pathways 109F to effectively shorten Li ion diffusion pathlengths for charge transfer, hierarchical pores 101A and/or open porousscaffold 102A may be created from reduced-size carbon particles and/oractive materials (down to nanometer scales), since the external specificsurface area (SSA, defined as the total surface area of a material perunit of mass, (with units of m²/kg or m²/g) or solid or bulk volume(units of m²/m³ or m⁻¹); it is a physical value that can be used todetermine the type and properties of a material (soil or snow)) of asphere increases with decreasing diameter. However, as the particle sizeis decreased down into the nanometer size range there are associatedattractive van der Waal forces that can impede dispersion, facilitateagglomeration, and thereby increase cell impedance and reduce powerperformance.

Another approach to shortening ion diffusional pathways, referring toion diffusion pathways 109F shown in FIG. 1F, is to uniquely engineerthe internal porosity of the constitutive carbon-based particles, suchas those created by the electrically conductive interconnectedagglomerations of graphene sheets 101B to create open porous scaffold102A and/or define hierarchal pores 101A and/or 107F. As per commonlyused definitions, and as referred to herein, a “surface curvature” isreferred to as a “pore” if its cavity is deeper than it is wide. As aresult, this definition necessarily excludes many nanostructured carbonmaterials where just the external surface area is modified, or in closepacked particles where voids (intra-particular) particular) are createdbetween adjacent particles (as in the case of a conventional slurry castelectrode).

With respect to the engineering (referring to the synthesis, creation,formation, and/or growth of mesoporous carbon-based particle 100A eitherin-flight in a microwave-based reactor or via layer-by-layer depositionin a thermal reactor as substantially described earlier), reactorprocess parameters may be adjusted to tune the size, geometry, anddistribution of hierarchical pores 101A and/or 107F within mesoporouscarbon-based particle 100A. Hierarchical pores 101A and/or 107F withinmesoporous carbon-based particle 100A may be tailored to achieveperformance figures particularly well-suited for implementation inhigh-performance performance fast-current delivery devices, such assupercapacitors.

As generally described earlier, a supercapacitor (SC), also called anultracapacitor, is a high-capacity capacitor with a capacitance valuemuch higher than other capacitors, but with lower voltage limits, thatbridges the gap between electrolytic capacitors and rechargeablebatteries. It typically stores 10 to 100 times more energy per unitvolume or mass than electrolytic capacitors, can accept and delivercharge much, much faster than batteries, and tolerates many more chargeand discharge cycles than rechargeable batteries.

In many of the available off-the-shelf commercial carbons used in earlysupercapacitor development efforts, there were “worm”-like narrow poreswhich became a bottleneck or liability when operating at high currentdensities and fast charge- and discharge rates, as electrons mayencounter difficulty in flow through, in or around such structures orpathways. Even though pore dimensions were fairly uniform but stilladjustable to accommodate a wide range of length scales, real-lifeachievable performance was still self-limited (as based on thestructural challenges inherent to the “worm”-like narrow pores).

Compared to conventional porous materials with uniform pore dimensionsthat are tuned to a wide range of length scales, the presently disclosed3D hierarchical porous materials (such as that shown by hierarchicalpores 101A and/or 107F within mesoporous carbon-based particle 100A) maybe synthesized to have well-defined pore dimensions (such ashierarchical pores 107F including pores 104F, 105F, and/or pathways 106Fand/or 109F) and topologies overcome the shortcomings of conventional‘mono-sized’ porous carbon particles by creating, multi-modal (such asbi-modal) pores and/or channels having the following dimensions and/orwidths:

-   -   (1) meso (2 nm<d_(pore)<50 nm) pores;    -   (2) macro (d_(pore)>50 nm) pores 301A (as shown in micrograph        300A of FIG. 3A) to minimize diffusive resistance to mass        transport; and,    -   micro (d_(pore)<2 m) pores 302A to increase surface area for        active site dispersion and/or ion storage (capacitance relating        to density and number of ions that can be stored within a given        pore size, such as that shown by pore 105F having dimension 103F        in FIG. 1F).

Although no simple linear correlation has been experimentallyestablished between: (1) surface area; and, (2) capacitance, mesoporouscarbon-based particle 100A offers surprising favorable results inproviding optimal micropore size distributions and/or configurations(such as when integrated into a Li ion or Li S battery electrode toachieve certain specific capacity and power values or ranges) that aredifferent for each intended end-use application (such as an electrolytesystem) and corresponding voltage window. To optimize capacitanceperformance, mesoporous carbon-based particle 100A may be synthesizedwith very narrow “pore size distributions” (PSD); and, as desired orrequired voltages are increased, larger pores are preferred. Regardless,current state-of-the-art supercapacitors have provided a pathway toengineering the presently disclosed 3D hierarchical structured materialsfor particular end-use applications.

In contrast to supercapacitors, where capacitance and power performanceis primarily governed by, for example:

-   -   (1) surface area of the pore wall;    -   (2) size of pore; and    -   (3) interconnectivity of the pore channels (which affect        electric double layer performance)

Li-ion storage batteries undergo faradaic reduction/oxidation reactionswithin the active material and thereby may require not only all of theLi ion transport features of a supercapacitor (such as efficientlyoriented and/or shortened Li ionic diffusion pathways). Regardless, inany application (including a supercapacitor as well as a traditional Liion or Li S secondary battery) a 3D nanocarbon-basedframework/architecture (such as that defined open porous scaffold 102A)can provide continuous electrical conducting pathways (such as acrossand along electrically conductive interconnected agglomerations ofgraphene sheets 101B) alongside, for example, highly-loaded activematerial having high areal and volumetric specific capacity.

Mesoporous Carbon-Based Particle—Used as a Formative Material for aCathode

To address prevailing issues with relatively low electrical and ionicconductivities, volume expansion and polysulfide (PS) dissolution(referring to the PS “shuttle” effect, discussed earlier, leading tolithium loss and capacity fade) in current sulfur cathode electrodedesigns, mesoporous carbon-based particle 100A has hierarchical pores101A and/or 107F formed therein to define open porous scaffold 102A,which includes pores 105F with microporous textures 103F having adimension (such as 1-4 nm cavities) suitable to at least temporarilymicro-confine elemental sulfur and/or Li S related compounds. Openporous scaffold 102A, at the same time as confining sulfur as sodescribed, also provides a host scaffold-type structure to manage sulfurexpansion to ensure surprising, unexpected, and highly desirableelectron transport across the sulfur-carbon interface (such as atcontact and/or interfacial regions of sulfur and carbon within pores105F) by, for example, tailored in-situ nitrogen doping of the carbonwithin the reactor. Confining sulfur within a nanometer scale cavity(such as pores 105F with microporous textures 103F) favorably altersboth:

-   -   (1) the equilibrium saturation (solubility product); and,    -   (2) crystalline behavior of sulfur, such that sulfur remains        confined (as may be necessary for desirable electrical        conduction upon dissociation of Li S compounds, etc.) within        microporous textures having dimension 103F, with no external        driving force required to migrate to the anode electrode.        As a result, unique dimension 103F (including diameter, height        and/or width of about 1-4 nm in cavity form as described above)        provided by pores 105F results in no need for separators that        attempt to impede polysulfide diffusion while, at the same time,        negatively impacting cell impedance (referring to the effective        resistance of an electric circuit or component to alternating        current, arising from the combined effects of ohmic resistance        and reactance) and polarization. By using carbon with optimum        (relative to elemental sulfur, lithium and/or Li S        micro-confinement) and non-optimum multi-modal, referring to        hierarchical pores 107F including pores 104F, 102F, and/or 103F,        or (alternatively) bi-modal pore distributions, mesoporous        carbon-based particle 100A demonstrates, unexpectedly and        favorably, operation of the principle of micro-confinement in        properly optimized (relative to final end-use application        specific demands) structures.

Along with creating delicately engineered ornate, hierarchicalmulti-modal carbon-based particles, such as mesoporous carbon-basedparticle 100A and organized scaffolds generated therefrom, mesoporouscarbon-based particle 100A further uniquely provides the ability toeffectively load or infuse carbon scaffold 300B shown in FIG. 3B (thatmay be created in-reactor by either:

-   -   (1) layer-by-layer deposition of multiple mesoporous        carbon-based particles 100A by a slurry-case method; or,    -   (2) by a continuous sequence of a group of plasma spray-torches,        as shown by plasma spray-torch system 400B in FIG. 4B), with        sulfur, such as elemental sulfur.

For lithium-sulfur battery performance to practically exceedconventional lithium ion batteries, industry-scalable techniques mustachieve high sulfur loading (such as >70% sulfur per unit volume)relative to all additives and components of a given cathode template,while maintaining the native specific capacity of the sulfur activematerial. Attempts to incorporate sulfur into a cathode host, such as byany one or more of (performed independently or in any combination):electrolysis, wet chemical, simple mixing, ball milling, spray coating,and catholytes, have either not fully incorporated the sulfur asdesirable, or are otherwise not economically scalable or manufacturable.Unlike melt infiltration where small pores are thermodynamicallyinaccessible, presently disclosed synthetic approaches use an isothermalvapor technique, introduced and reacted at substantially atmosphericpressure, where the high surface free energy of nanoscale pores orsurfaces drives the spontaneous nucleation of sulfur containing liquidsuntil a conformal coating of sulfur and/or lithium-containing condensateis reached on inner-facing surfaces of hierarchical pores 101A and/or107F. In essence, unique vapor infusion process unexpectedly (andfavorably) completely infuses sulfur into fine pores (such as any one ormore of hierarchical pores 101A and/or 107F and/or pores 104F, 105Fand/or pathways 106F and/or 109F) at the core of mesoporous carbon-basedparticle 100A, and therefore not just at its surface.

Mesoporous Carbon-Based Particle to create an Electrically ConductiveScaffold

Mesoporous carbon-based particle 100A, may be fabricated any number ofways using both known and novel techniques disclosed herein, including:

-   -   (1) slurry-casting, referring to conventional metalworking,        manufacturing and/or fabrication techniques in which a liquid        material is usually poured into a mold, which contains a hollow        cavity of the desired shape, and then allowed to solidify; or    -   (2) plasma spray-torch system 400B (shown in FIG. 4B), which may        be used to perform layer-by-layer deposition to grow mesoporous        carbon-based particle 100A incrementally.

Either (1) or (2) as described above, or any other known or novelfabrication techniques, may be used to create carbon scaffold 300B in a“graded” manner, referring to under specifically controlled conditionsresulting in corresponding control of:

-   -   (1) electrical gradients (referring to interconnected 3D        agglomerations of multiple layers of graphene sheets 101B that        are sintered together, as discussed earlier, to form open porous        scaffold 102A that facilitates electrical conduction along and        across contact points of graphene sheets 101B); and,    -   (2) ionic conductive gradients (referring Li ion transport        through hierarchical pores 101A and/or 107F, which are defined        by electrically conductive interconnected agglomerations of        graphene sheets 101B, and cause rapid lithium (Li) ion diffusion        effectively shortening Li ion diffusion pathways 109F)        throughout thickness of carbon scaffold 300B, in the vertical        height direction A as shown in FIG. 3B, of mesoporous        carbon-based particle 100.

Reference is made herein to various forms of carbon and/or graphenesynthesized in-flight within a reactor (or reaction chamber)substantially as described earlier to create electrically conductiveinterconnected agglomerations of graphene sheets 101B, which may vary inshape, size, position, orientation, and/or structure. Such variances areinfluenced in differences in crystallinity and the particular type ofcarbon allotrope(s) used for creation of electrically conductiveinterconnected agglomerations of graphene sheets 101B. “Crystallinity”,as generally understood and as referred to herein, implies the degree ofstructural order in a solid. In a crystal, atoms or molecules arearranged in a regular, periodic manner. The degree of crystallinitytherefore has a significant influence on hardness, density, transparencyand diffusion.

Mesoporous carbon-based particle 100 can be produced in the form of anorganized scaffold, such as a carbon-based scaffold, out of a reactor(including thermal or microwave-based reactor) or be created (at leastpartially) during post-processing activities taking place outside ofprimary synthesis within a reactor.

Plasma processing and/or plasma-based processing, may be conductedwithin a reactor as disclosed by Stowell, et al., “Microwave ChemicalProcessing Reactor”, U.S. Pat. No. 09,767,992, (Sep. 19, 2017), wheresupply gas is used to generate a plasma in the plasma zone to convert aprocess input material (such as methane and/or other suitablehydrocarbons in a gaseous phase) into separated components in a reactionzone (such as a reaction chamber) to facilitate in-flight synthesis ofcarbon-based materials, including mesoporous carbon-based particle 100Agrown to create carbon scaffold 300B at approximately 1 atmosphere.

Alternative to synthesis by or within a microwave reactor as describedabove, thermal energy may be directed toward or near carbon-containingfeedstock materials supplied in a gaseous phase onto sacrificialsubstrate 306B to sequentially deposit multiple layers of mesoporouscarbon-based particles 100A by, for example, plasma spray-torch system400B shown in FIG. 4B. Such particles may be either fused togetherin-flight (in a microwave reactor) or deposited (in a thermal reactor)in a controlled manner to achieve varying concentration levels ofcarbon-based particles 100A to therefore, in turn, achieve “graded”electrical conductivity proportionate to concentration levels ofmesoporous carbon-based particles 100A. Such procedures may be used toformulate porous carbon-based electrode structure (such as carbonscaffold 300B) that has a high degree of tunability (regardingelectrical conductivity and ionic transport) while also eliminating manyproduction steps and otherwise retaining a conventional outwardappearance.

An objective of producing mesoporous carbon-based particle 100A out of,for example, a microwave reactor, includes producing open porousscaffold 102A with an open cellular structure such that a liquid-phaseelectrolyte can easily infiltrate into the pores of mesoporouscarbon-based particle 100A via (at least) open porous scaffold 102A. Asgenerally understood and as referred to herein, a “porous medium” or a“porous material” refers to a material containing pores, also referredto herein as “voids”. Skeletal portions of open porous scaffold 102A maybe referred to as a “matrix” or a “frame”, and pores (such ashierarchical pores 101A and/or 107F) can be infiltrated with a fluid(liquid or gas), whereas, skeletal material is usually formed as a solidmaterial.

Porosity of the Mesoporous Carbon-Based Particle—in Detail

A porous medium, such as mesoporous carbon-based particle 100A, can becharacterized by its porosity. Other properties of the medium (such aspermeability, tensile strength, electrical conductivity, and tortuosity)may be derived from the respective properties of its constituents (ofsolid matrix and fluid interspersed therein), as well as media porosityand pore structure. Mesoporous carbon-based particle 100A can be createdout of a reactor (and possibly also subsequently post-processed, to bediscussed in detail herein) to achieve desirable porosity levels thatare unexpectedly conducive for ion diffusion (such as Li ion), whereascontacting electrically conductive interconnected agglomerations ofgraphene sheets 101B facilitate electron conduction while also allowingfor electrons to reunite with positive ions at reaction sites.

Regarding, porosity and tortuosity of open porous scaffold 102A ofmesoporous carbon-based particle 100A, an analogy may be made to marblesin a glass jar. Porosity, in this example, refers to spacing between themarbles that allows liquid-phase electrolyte to penetrate into voidspaces between the marbles, similar to hierarchical pores 107F thatdefine ion diffusion pathways 109F. The marbles themselves may be likeswiss cheese, by allowing electrolyte not only to penetrate in cracksbetween agglomerations of graphene sheets 101B, but also intoagglomerations of graphene sheets 101E themselves. In this example aswell as others, the relative “shortening” of ion diffusion pathways 109Frefers to how long it takes Li ions infiltrated therein by, for example,capillary action to contact active material (such as S confined withinpores 105F). Ion diffusion pathways 109F accommodate convenient andrapid infiltration and diffusion of electrolyte, that may contain Liions, into mesoporous carbon-based particle 100A, synthesized further tocreate carbon scaffold 300B with graded electric conductivity.

The “shortening” of ion diffusion pathways 109F refers toward theshortening of diffusion lengths through which Li ions move within openporous scaffold 102A in carbon scaffold 300B and not active materialitself (as it is commonly understood that the diffusion length of theactive material may be shortened only by making the thickness of theactive material lesser or smaller). Ion diffusion pathways 109F can actas ion buffer reservoirs by controlling flow and/or transport of ionstherein to provide a surprisingly favorable freer flowing structure forion transport therein, as may be beneficial for ion confinement andtransport during electrochemical cell charge-discharge cycles. Transportof Li ions throughout ion diffusion pathways 109F in the generaldirections shown in FIG. 1F can take place in a liquid electrolyteinitially infused and captured within open porous scaffold 102A, wheresuch infusion of electrolyte occurs prior to cyclic carbon scaffold 300Busage. Alternatively, examples exist permitting for the initialdiffusion and distribution of liquid-phase electrolyte in open porousscaffold 102A of mesoporous carbon-based particle 100A to fill up andoccupy hierarchical pores 101A and/or 107F prior to usage of carbonscaffold 300B, synthesized or otherwise created by layer-on-layerdeposition of mesoporous carbon-based particles 100A. In alternative oraddition to substantially complete filling of open porous scaffold 102Awith electrolyte as described, vacuum or air may also be used to atleast partially fill hierarchical pores 101A and/or 107F, which mayallow or assist with wetting of electrolyte with carbon-containingexposed surfaces within open porous scaffold 102A (to be describedfurther herein).

Once an electrode is formed using carbon scaffold 300B, throughadditional exposure and electrochemical reactions, Li ions actuallybounce from one location to another by a chain reaction, similar to thestriking of “newton” balls, where one hits to result in forcetransference resulting in the movement of other balls. Similarly, eachLi ion moves a relatively short distance, yet remains able to move greatnumbers of Li ions in the collective through this type of chain reactionas described. The extent of individual Li ion movement may be influencedby the quantity of Li ions supplied altogether to carbon scaffold 300Bvia capillary infusion into open porous scaffold 102A, as may be thecrystallographic arrangement of Li ions and/or particles in, around, orwithin agglomerations of graphene sheets 101B.

Electrochemical Cell Electrode (Anode or Cathode) Created from CarbonScaffold

Carbon scaffold 300B can be functionally integrated in a variety ofbattery or supercapacitor applications, battery types including Li ionbatteries and Li S batteries, as well as Li air cathodes, upon suitabledevelopment. Such an example battery system may include anelectrochemical cell configured to supply electric power to a system.The electrochemical cell may have an anode containing an anode activematerial, a cathode containing a cathode active material, a porousseparator disposed between the anode and the cathode, and an electrolytein ionic contact with the anode active material and the cathode activematerial.

The anode and cathode may include sacrificial substrate 306B (that iselectrically conductive), with a first layer deposited there-upon as afirst contiguous film having a first concentration of mesoporouscarbon-based particles 100A and/or 302B, each mesoporous carbon-basedparticle 100A and/or 302B contacting another and being composed ofelectrically conductive interconnected 3D aggregates of graphene sheets101B. Aggregates of graphene sheets 101B are sintered together to formopen porous scaffold 102A (shown in FIG. 1A) that facilitates electricalconduction along and across contact points of the graphene sheets 101B.Open porous scaffold 102A has a 3D hierarchical structure with mesoscalestructuring in combination with micron-scale fractal structuring, anyone or more further featuring minute carbon-based particles 304Binterspersed in and/or between adjacent carbon-based particles 100Aand/or 302B.

A porous arrangement is formed in open porous scaffold 102A. The porousarrangement is conducive to receive electrolyte dispersed therein forion (such as Li ion) transport through interconnected hierarchical pores101A and/or 107F that define one or more channels including:

-   -   (1) microporous frameworks defined by a dimension 101F of >50 nm        that provide tunable Li ion conduits;    -   (2) mesoporous channels defined by a dimension 101F of about 20        nm to about 50 nm (generally defined under IUPAC nomenclature        and referred to as “mesopores” or “mesoporous”) that act as Li        ion-highways for rapid Li ion transport therein; and    -   (3) microporous textures defined by a dimension 103F of <4 nm        for charge accommodation and/or active material confinement.

The first layer including a first electrical conductivity ranging from500 S/m to 20,000 S/m. A second layer is deposited on the first layer.The second layer has a second contiguous film with a secondconcentration of mesoporous carbon-based particles 100A in contact witheach other to yield a second electrical conductivity ranging from 0 S/mto 500 S/m (lower than the first electrical conductivity).

Carbon scaffold 300B may be pre-lithiated and later infused with Li ionliquid solution via capillary action to create lithiated carbon scaffold400A (to be further explained herein) as shown in FIG. 4A. Interimlayers 406A, 408A, 410A, and 412A (having defined thicknesses in thevertical direction extending from the current collector, which may be asacrificial and/or electrically conductive substrate, toward electrolytelayer 414A) may be synthesized in-flight in a microwave reactor, ordeposited layer-by-layer in or out of a thermal reactor. Interim layers406A, 408A, 410A, and 412A have varying electrical conductivity rangingfrom high (such as at interim layer 406A) to low (such as at layer 412A)in a direction orthogonal and away from the current collector, which mayalso be a sacrificial and/or electrically conductive substrate. Varyingelectrical conductivity may be at least partially proportionate tointerfacial surface tension of a Li ion solution infiltrated into theporous arrangement of the open porous scaffold, where infiltration ofthe Li ion solution is done via capillary infusion engineered to promotewetting (to be further explained herein) of surfaces of open porousscaffold 102A exposed to Li ion solution, as well as the prevalence(concentration) of conductive carbon particles 404A interspersed withinmesoporous carbon-based particles 402A (that are equivalent or similarto mesoporous carbon-based particles 100A, 100E and/or the like).

Li ion diffusion pathways 109F (as shown in FIG. 1F) ensure thatdeposition and stripping operations associated with one or moreoxidation-reduction (“redox”) reactions occurring within mesoporouscarbon-based particles 100A and/or 302B are uniform. Also, anode activematerial and/or cathode active material resides in pores of the anodeand the cathode, respectively, and may contain single-layer graphene(SLG) and/or few-layer graphene (FLG) including from 1 to 10 grapheneplanes, respectively, the graphene planes being positioned in asubstantially aligned orientation along a vertical axis. Anode activematerial or cathode active material may have a specific surface areafrom approximately 500 m²/g to 2,675 m²/g when measured in a driedstate, and may contain a graphene material comprising any one or more ofpre-lithiated graphene sheets, pristine graphene, graphene oxide,reduced graphene oxide, graphene fluoride, graphene chloride, graphenebromide, graphene iodide, hydrogenated graphene, nitrogenated graphene,boron-doped graphene, nitrogen doped graphene, chemically functionalizedgraphene, physically or chemically activated or etched versions thereof,conductive polymer coated or grafted versions thereof, and/orcombinations thereof.

In any one or more of the discussed examples in relation to lithiatedcarbon scaffold 400A, electrically conductive interconnectedagglomerations of graphene sheets 101B are sintered together to formopen porous scaffold independent of a binder, however alternativeexamples do exist where a binder is used. Configurations with or withouta binder may each involve open porous scaffold 102A acting or serving asan active lithium intercalating structure with a specific capacity ofapproximately 744-1,116 mAh/g, or more. Also, examples include thepreparation of electrically conductive interconnected agglomerations ofgraphene sheets 101B using chemically functionalized graphene, involvingthe surface functionalization thereof, comprising imparting to openporous scaffold 102A a functional group selected from quinone,hydroquinone, quaternized aromatic amines, mercaptan, disulfide,sulfonate (—SO₃), transition metal oxide, transition metal sulfide,other like compounds or a combination thereof.

The current collector shown in FIG. 4A, is, for example, at leastpartially foam-based or foam-derived and is can be selected from any oneor more of metal foam, metal web, metal screen, perforated metal,sheet-based 3D structure, metal fiber mat, metal nanowire mat,conductive polymer nanofiber mat, conductive polymer foam, conductivepolymer-coated fiber foam, carbon foam, graphite foam, carbon aerogel,carbon xerogel, graphene foam, graphene oxide foam, reduced grapheneoxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphitefoam, and combinations thereof.

Anode or cathode electrically conductive or insulative material,referred to herein as “active material” can include any one or more ofnanodiscs, nanoplatelets, nano-fullerenes, carbon nano-onions (CNOs),nano-coating, or nanosheets of an inorganic material selected from: (i)bismuth selenide or bismuth telluride, (ii) transition metaldichalcogenide or trichalcogenide, (iii) sulfide, selenide, or tellurideof a transition metal; (iv) boron nitride, or (v) a combination thereof.The nanodiscs, nanoplatelets, nano-coating, or nano sheets can have athickness less than 100 nm. In similar or dissimilar examples, thenanoplatelets can have a thickness less than 10 nm and/or a length,width, or diameter less than 5 μm.

Processes for Producing an Electrochemical Cell Electrode (Anode orCathode) Created from Carbon Scaffold—Generally

Example processes for producing a three-dimensional (3D) mesoporouselectrode, such as that created from lithiated carbon scaffold 400A, caninclude depositing (such as from one or more plasma-based thermalreactors or torches, in which thermal energy is propagated through aplasma and/or feedstock material supplied in a gaseous state) mesoporouscarbon-based particles 100A or 400A to form a first contiguous filmlayer (such as layer 406A shown in FIG. 4A) on a substrate, where thefirst contiguous film layer is characterized by a first electricalconductivity. Each of the mesoporous carbon-based particles compriseselectrically conductive three-dimensional (3D) aggregates oragglomerations of graphene sheets 101B. The aggregates are sinteredtogether to form open porous scaffold 102A that facilitates electricalconduction along and across contact points of the graphene sheets. Aporous arrangement formed in open porous scaffold 102A, where the porousarrangement is conducive to receive electrolyte dispersed therein for Liion transport through interconnected pores (such as hierarchical pores101A and/or 107F) that define one or more Li ion diffusion pathways109F. The first contiguous film layer has an average thickness nogreater than approximately 100-200 μm. In an example, a binder materialis combined with graphene sheets 101B to retain graphene sheets 101B ina desired position to impart structure to open porous scaffold 102A. Thebinder may be or comprise a thermosetting resin or a polymerizablemonomer, wherein curing the resin or polymerizing the polymerizablemonomer forms a solid resin or polymer with assistance of heat,radiation, an initiator, a catalyst, or a combination thereof. Thebinder may be initially a polymer, coal tar pitch, petroleum pitch,mesa-phase pitch, or organic precursor material and is later thermallyconverted into a carbon material.

Additional quantities of mesoporous carbon-based particles 101A and/or400A are deposited on the first contiguous film layer to form a secondcontiguous film layer there-upon, the second contiguous film layerhaving a second electrical conductivity lower than the first electricalconductivity, and being positioned closer to electrolyte 414A and awayfrom the current collector (which may be a sacrificial substrate).

Li ion solution can be infiltrated into (such as by capillary infusionaction) open porous scaffold 102A react with exposed carbon on surfacesthereof to facilitate Li ion dissociation and electric current supply,where the exposed carbon on the open porous scaffold including a surfacearea greater than approximately 100 m²/gm.

Processes for Producing an Electrochemical Cell Electrode (Anode orCathode) Created from the Carbon Scaffold—In Detail

Mesoporous carbon-based particles 100A and/or lithiated carbon scaffold400A can be synthesized ‘in-flight’ in a microwave reactor, or depositedin a bottom-up manner, referring to a layer-by-layer deposition or“growth” within a thermal reactor, and may then be cast, via a liquidslurry to be subsequently dried to form a carbon-based electrode thatmay be suitable for implementation or incorporation within a Li ionbattery. Such a slurry may, in some examples, comprise chemical bindersand conducting graphite, along with the electrochemically active innatecarbon.

The term “hierarchical”, as generally understood in an engineeringcontext and as used herein, refers to an arrangement of items in whichthe items are represented as being above, below, or at the same level asone another. Here, mesoporous carbon-based particle 100A and/orlithiated carbon scaffold 400A may be grown by layer-by-layer depositionin a thermal reactor to create one or more “grades” (as indicated bylayers 406A to 412A of mesoporous conductive particles 100A, 302B and/or402A), referring to that created by specific control of electrical(referring to contact points of electrically conductive interconnectedagglomerations of graphene sheets 101B) and ionic (referring to Li iondiffusion pathways 109F) conducting gradients throughout the thicknessof lithiated carbon scaffold 400A. Tuning of each individually depositedlayer 406A through 412A results in relatively higher electricalconductivity at the current collector interface, and progressive lowerelectrical conductivity moving outwardly therefrom.

Electrically conductive interconnected agglomerations of graphene sheets101B within mesoporous carbon-based particle 100A serve as bothelectrical conductors, by conducting electric current through contactpoints and/or regions, and as “active” Li intercalating structures, andtherefore may be configured to provide a source for the specificcapacity of the anode electrode at 744-1,116 mAh/g, i.e., 2-3 times thatotherwise available from conventional graphite anodes at 372 mAh/g. As aresult, interconnected 3D bundles of graphene sheets 102 withinmesoporous carbon-based particle 100 may be considered as ‘nanoscale’electrodes that concurrently enable a relatively high-volume fraction ofelectrolytically active material along with efficient, 3Dinterpenetrating, ion and electron pathways.

This unique 3D structure of mesoporous carbon-based particle 100 enablesboth storage of electric charge at its exposed surfaces (via capacitivecharge storage) for desirable high-power delivery, relative toconventional applications, and also provides faradaic redox ions withinthe bulk thereof for desirable high electric energy storage. “Redox”, asgenerally understood and as referred to herein, refers to“reduction-oxidation” reactions in which the oxidation states of atomsare changed involving the transfer of electrons between chemicalspecies, most often with one species undergoing oxidation while anotherspecies undergoes reduction.

“Faradaic”, as generally understood and as referred to herein, refers toa heterogeneous charge-transfer reaction occurring at the surface of anelectrode, prepared with and/or otherwise incorporating mesoporouscarbon-based particle 100A. For instance, pseudocapacitors storeelectrical energy faradaically by electron charge transfer betweenelectrode and electrolyte. This is accomplished through electrosorption,reduction-oxidation reactions (redox reactions), and intercalationprocesses, termed pseudocapacitance.

Roll-to-Roll Processing for Producing an Electrochemical Cell Electrode(Anode or Cathode) Created from the Carbon Scaffold

Regarding manufacturing, lithiated carbon scaffold 400A can bemanufactured (to fabricate and/or build electrochemical cell electrodes,such as cathodes and/or anodes) in large-scale quantities by sequential,layer-by-layer (such as layers 406A through 412A shown in FIG. 4A)deposition of concentrations of mesoporous carbon-based particle 100Aand/or 100E onto a moving substrate (such as a current collector)through a roll-to-roll (“R2R”) production approach. By consolidating 3Dcarbon scaffold structures directly out microwave reactors (analogous toexiting plasma spray processes), electrode films can be continuouslyproduced without the need for toxic solvents and binders that areotherwise used in slurry cast processes for battery electrodes.Therefore, battery electrodes employing lithiated carbon scaffold 400Amay be more readily produced with controlled electrical, ionic, andchemical concentration gradients due to the “layer-by-layer”, sequentialparticle deposition capabilities of a plasma-spray type processes; and,specific elements (such as dopants) can also be introduced at differentstages within the plasma deposition process.

Also, due to the pores 101A and/or 107F interspersed throughoutmesoporous carbon-based particle 100, lithiated carbon scaffold 400A maybe manufactured in a manner such that it is gravimetrically, referringto a set of methods used in analytical chemistry for the quantitativedetermination of an analyte based on its mass, superior to knowndevices. That is, mesoporous carbon-based particle 100A, with poresand/or voids defined throughout 3D bundles of graphene sheets 102 and/orconductive carbon particles 104, may be lighter than comparable batteryelectrodes without a mesoporous structure including various pores and/orvoids, etc.

Mesoporous carbon-based particle 100 may feature a ratio of activematerial to inactive material that is superior relative to conventionaltechnologies, in that greater quantities of active material areavailable and prepared for electricity conduction there-through relativeto inactive and/or structural reinforcement material. Such structuralreinforcement material, although involved in defining a generalstructure of mesoporous carbon-based particle 100A, may not be involvedor as involved in electrically conductive interconnected agglomerationsof graphene sheets 101B. Accordingly, due to its high active material toinactive material ratio, mesoporous carbon-based particle 100A maydemonstrate superior electrical conductivity properties relative toconventional batteries, as well as being significantly lighter than suchconventional batteries given that carbon may be used to replacetraditionally used heavier metals. Therefore, mesoporous carbon-basedparticle 100A may be particular well-suited for demanding end-useapplication areas that also may benefit from its relatively lightweight, automobiles, light trucks, etc.

Mesoporous carbon-based particle 100A may be created to relyelectrically conductive interconnected agglomerations of graphene sheets101B to obtain a percolation threshold, referring to a mathematicalconcept in percolation theory that describes the formation of long-rangeconnectivity in random systems. Below the threshold a giant connectedcomponent does not exist, while above it, there exists a giant componentof the order of system size. Accordingly, 3D bundles of grapheneelectrically conductive interconnected agglomerations of graphene sheets101B may conduct electricity from the current collector, as shown inFIG. 4A, toward electrolyte 414A.

Roll-to-Roll (“R2R”) Plasma Spray Torch Deposition System

As a variation from the existing atmospheric MW plasma reactor withparticle-based output, integrated, contiguous 3D hierarchical carbonscaffold films (composed of multiple mesoporous carbon-based particles100A and/or the like agglomerated together and/or contacting to formcontiguous layers, films, and/or sheets) can be constructed utilizing aspray torch configuration, such as that shown by roll-to-roll (“R2R”)system 400 b. Plasma torches (generally) permit for materials to beinitially formulated, similar to waveguided reactor, then acceleratedinto an impact zone on a substrate surface (moving or stationary)wherein each zone can provide for unique control of dissimilar (mixedphase or composite) material synthesis, formulation (consolidation), andintegration (densification).

The plasma torch in combination with a continuous, moving substrateenable a unique additive type process control (i.e., both within the hotplasma and beyond the plasma afterglow region up to the impact zone ofthe substrate) of properties, such as defect density, residual stress,through thickness chemical and thermal gradients, phase transformations,and anisotropy. For the case of battery electrode fabrication, not onlycan the atmospheric MW plasma torch create formulated and integratedcontinuous 3D hierarchical mesoporous graphene films without the needfor toxic solvents such as NMP and or use of binders and conductivecarbons (at the very least reduction) in accordance with the slurrycasting process, but the plasma torch can be used to create integratedelectrode/current collector film structures for enhanced performance ata reduced cost.

FIG. 4B shows in detail roll-to-roll (“R2R”) system 400 b employing anexample arrangement of a group 444B of plasma spray torches 422B through428B (such as 422B, 424B, 426B, and/or 428B) configured to performlayer-by-layer deposition to fabricate, otherwise referred to as“growing”, carbon-based scaffold 300B, shown in FIG. 3B, and/or variantsthereof, incrementally. Group 444B of plasma spray torches 414B through420B are oriented in a continuous sequence above the R2R processingapparatus 440B, which, may include wheels and/or rollers 434B and 439Bconfigured to rotate in the same direction, 430B and 432B, respectively,to result in translated forward motion 436B of sacrificial layer 402Bupon which layers 442B of carbon scaffold 436B may be deposited in alayer-by-layer manner to achieve a “graded” electrical conductiongradient proportionate to the concentration level of mesoporouscarbon-based particles 100A contained per unit volume area in eachprogressive deposited layer (such as interim layers 406A-412A).

Such deposition may involve the positioning of group 444B of plasmaspray torches 414B through 420B as shown in FIG. 4B, with an initial, indirection of forward motion 436B, spray torch 414B extending thefurthest in a downward direction, toward sacrificial layer 404B fromfeedstock supply line 412B, positioned to spray 422B carbon-basedmaterial to deposit initial layer 404B (also may be shown as interimlayer 406A in FIG. 4A, and so on and so forth) of carbon scaffold 300Bon sacrificial layer 402B. Initial layer 404B may be deposited toachieve the highest conductivity values, with each of the subsequentlayers 406B through 410B featuring a proportionately less-densedispersion of mesoporous carbon-based particle 100A composingcarbon-based scaffold 300B to achieve a ‘graded’ electric gradient forlayers 442B.

That is, plasma spray torches 414B through 420B may be oriented to haveincrementally decreasing (or otherwise varying) heights as shown in FIG.4B, such that each spray torch from group 444B may be tuned to spray,from spray 422B to 428B, respectively, sprays of carbon-based feedstockmaterial supplied by feedstock supply line 412B. Accordingly, batteryelectrodes can be more readily produced with controlled electrical,ionic, and chemical concentration gradients due to the “layer-by-layer”,sequential deposition described herein with connection to plasmaspray-torch system 400B, which presents desirable features of plasmaspray type processes; and, specific elements or additional ingredientscan also be introduced at different stages within the plasma-based spraydeposition process described by plasma spray-torch system 400B. Suchcontrol may, extend to tunability of plasma spray-torch system 400B toachieve target electric field and/or electromagnetic field properties ofany one or more of layers 442B.

Group 444B of plasma spray torches 414B through 420B may employplasma-based thermally enhanced carbon spraying techniques to providecarbon coating processes in which melted (or heated) materials aresprayed onto a surface. The “feedstock” (coating precursor) is heated byelectrical (plasma or arc) or chemical means (combustion flame).

Thermal spraying by plasma spray torches 414B through 420B can providethick coatings (approx. thickness range is 20 μm or more to several mm,depending on the process and feedstock), over a large area at highdeposition rate as compared to other coating processes such aselectroplating, physical and chemical vapor deposition. Coatingmaterials available for thermal spraying include metals, alloys,ceramics, plastics and composites. They are fed in powder or wire form,heated to a molten or semi-molten state and accelerated towardssubstrates in the form of μm -size particles. Combustion or electricalarc discharge is usually used as the source of energy for thermalspraying. Resulting coatings are made by the accumulation of numeroussprayed particles. The surface may not heat up significantly, allowingthe coating of flammable substances.

Coating quality is usually assessed by measuring its porosity, oxidecontent, macro and micro-hardness, bond strength and surface roughness.Generally, the coating quality increases with increasing particlevelocities.

Carbon Scaffold Implemented in a Li S Secondary Battery

Group 444B of plasma spray torches 414B through 420B may be configuredor tuned to spray carbon-based material in a controlled manner toachieve specific desired hierarchical and organized structures, such asopen porous scaffold 102A of mesoporous carbon-based particle 100Aand/or 100E with hierarchical pores 107F suitable to be used for Li ioninfiltration via capillary action therein dependant on percentageporosity of mesoporous carbon-based particle 100A and/or 100E. Totalquantities of S able to be infused into hierarchical pores 107F and/ordeposited on exposed surface regions of mesoporous carbon-based particle100A and/or 100E (and other such similar structures) may depend on thepercentage porosity thereof as well, where 3D fractal-shaped structuresproviding larger pores, such as pores 105F, each having dimension 103Fcan efficiently accommodate and micro-confine S for desired time-framesduring electrochemical cell operation. Examples exist permitting for thecombination of S to prevent any resultant polysulfides (PS) migratingout of pores 105F purely by designing and growing structural S, withconfinement of S being targeted at a defined percentage, such as: 0-5%,0-10%, 0-30%, 0-40%,0-50%, 0-60%, 0-70%, 0-80%, 0-90%, and/or 0-100%,any one or more of such ranges successfully showing of retardation ofpolysulfide migration out of the electrode structure.

Carbon Scaffold Implemented in a Li Air Secondary Battery

Existent Li air cathodes may last only 3-10 cycles, and thus have notyet been universally understood to provide very promising or reliabletechnologies. In such cathodes, air itself acts as the cathode,therefore the reliable and robust supply of air flowing through thecathode, such as through pores, orifices, or other openings, effectivelycurrently precludes realistic applications in consumer grade portableelectronic devices such as smartphones.

Devices can be made with some sort of air pump mechanism, but airpurification remains an issue, given that any amount of impurityprevalent in the air can and will react with available Li in parasiticside-reactions ultimately degrading specific capacity of the overallelectrochemical cell. Moreover, air only provides only about 20.9% O₂,and thus is not as efficient as other alternative current advancedbattery technologies.

Nevertheless, even in view of the above-mentioned challenges, examplesprovided above relating to mesoporous carbon-based particle 100A, 100Eand/or any variants thereof implemented in carbon scaffold 300B and/orlithiated carbon scaffold 400A can be configured to function in a3D-printed battery. Notably, measures can be taken to guard against,such as by tuning to achieve desirable structural reinforcement incertain targeted areas of open porous scaffold 102A, to prevent againstunwanted and/or sudden collapse of porous structures, such as to create‘clogging’ of passageways defined therein. In example, carbon scaffold300B can be decorated with a myriad of metal oxides to achieve suchreinforcement, which may also control or otherwise positive contributeto mechanical tunnelling of the structure itself once lithium reactswith air to spontaneously form a solid from that state, etc. Traditionalcircumstances (such as absent special preparations undertaken regardingimplementation of the disclosed mesoporous carbon-based particle 100Aand/or the like with Li air cathodes) can otherwise involve Li ionsreacting with carbon provided in a gaseous state, such that the Li ionand the carbon-containing gas react to form a solid that expands. And,depending on where this expansion occurs, can mechanically degrade theoverall carbon-based mesoporous scaffold structure, such as of carbonscaffold 300B.

Pre-Lithiation of 3D Mesoporous Carbon-Based Particle as a “Host”

To enable alternative non-lithium or lithiated carbon-based scaffoldedcathodes, such as those confining sulfur, oxygen, and vanadium oxide,over current lithium oxide compound cathodes, as well as to accommodatefirst charge lithium loss (resulting reduced coulombic efficiency) incurrent lithium-ion cells, a scalable pre-lithiation method forcarbon-based structured intended for implementation in electrochemicalcell electrodes may be required. As a result, various experimentalattempts have been conducted with mesoporous carbon-based particle100A,100E and/or any derivative structures based therefrom, includingcarbon scaffold 300B such as ball milling, post thermal annealing, andelectrochemical reduction from an additional electrode. Such effortshave been used to “pre-lithiate”, referring to chemically preparing acarbon-based structure to physically and/or chemically react with and/orconfine lithium, but have met with uniformity, lithium reactivity,costs, and scalability challenges.

Nevertheless, by fine-tuning reactor process parameters, 3D mesoporouscarbon-based particle 100A, 100E, and/or carbon scaffold 300B may besynthesized and/or fabricated by layer-by-layer deposition process, assubstantially discussed earlier, to serve as a carbon-based ‘host’structure with engineered surface chemistry (such as including nitrogenand oxygen doping) to facilitate rapid decomposition (involvingdisproportionation of oxides).

Upon thermal (referred to herein as “spark”) activation, Li metal can bespontaneously (such as without a pressure gradient) and non-reactivelyinfiltrated (driven by capillary forces) to create a controlled,pre-lithiated carbon structure (or particle building blocks).Subsequently, such “pre-lithiated” particle building blocks can besynthesized into an integrated composite film with graded electricalconductivity from:

-   -   (1) a high conductivity at a back plane in contact with the        current collector (such as shown by interim layer 406A, to    -   (2) an insulated ion conducting layer at the        electrolyte/electrode plane. Surface chemistry, as may be        related to non-reactive infiltration of Li metal can be tuned by        optimizing oxide thermal reduction degree (exotherm) by using        thermogravimetric analysis (TGA) or differential scanning        calorimetry DSC analytical techniques.

To address scalability concerns as may be related to transitioning froma low-volume laboratory testing and sample production environment, to ahigh-volume large-scale plant capable of fulfilling multiple customerorders simultaneously, the above described “pre-lithiation” process isreadily adaptable to a continuous roll-to-roll (R2R) format, analogousto other liquid melt wetting processes such as brazing.

Thin film lithium clad foil (tantalum or copper), can be loaded onto aheated calendaring roll, to be brought into contact with 3D mesoporouscarbon-based particle 100A and/or the like pre-form (or carbon film, inthe case of the spray torch process) in a controlled thermal, dryenvironment. Thermal residence (soak) time, gradient, and appliedpressure can adjusted and controlled to facilitate both: (1) “spark”activation; and, (2) infiltration process steps.

“Spark” Lithiation of the Carbon Scaffold

Historically, prior to the development of Li metal infusion methods intocarbon-based structures and/or agglomerate particles, efforts wereundertaken to assess the following two scenarios:

-   -   (1) growing microwave graphene sheets that have extended        de-spacing that would allow intercalation to occur in-between        individual graphene sheets at a much more efficient or a faster        rate than what would occur in typical, commercially-available,        graphene sheets; and, growing FLG in such a way to successfully        and repeatably achieve such higher de-spacing; and    -   (2) using a wet liquid Li metal front that propagates into        hierarchical pores 101A and/or 107F defined by open porous        scaffold 102A of 3D mesoporous carbon-based particle 100A and/or        100E. Attraction from Li metal to exposed carbon-based surfaces        wet the same in an efficient way relative to otherwise        performing functionalization on exposed carbon-based surfaces.

Presently disclosed examples relating to thermal reactors furtherprovide for capabilities for post processing to create highly organizedand structured carbons that have that particular functioning relating tothe infiltration of metal and/or other species, such as infiltration ofaluminum into a silicon carbide-sintered material, and hammering thesurface of the particles to promote infiltration of a molten (Li) metalfront without additional pressure from outside sources. Such effortspermit for continuous wetting instead of using pressure to push metalinto open porous scaffold 102A of 3D mesoporous carbon-based particle100A and/or 100E.

FIG. 4A shows a schematic representation of agglomerations oraggregations of 3D mesoporous carbon-based particles 402A, akin to 3Dmesoporous carbon-based particles 100A and/or 100E, synthesized ordeposited at varying concentration levels in layers 406A to 412A, frommost concentrated to least concentrated. All layers 406A through 412A,subsequent to creation, can be infiltrated, via non-reactive capillaryinfusion methods, with Li metal and/or Li ion solution in liquid stateor phase for intercalation of Li ions in-between individual graphenesheets of electrically conductive interconnected agglomerations ofgraphene sheets 101B of 3D mesoporous carbon-based particle 100A, whichmay be created with a spacing of 1 to 3 Å to accommodate more Li ionsbetween alternating graphene sheets when compared to conventionalcommercially available graphene sheet stacks.

Voids (referring to vacant regions or spaces) between adjacent and/orcontacting mesoporous carbon-based particles 100A and/or 100E composingany one or more of layers 406A-412A of lithiated carbon scaffold 400Amay be encased or at least partially covered by, at a section oflithiated carbon scaffold 400A positioned away from the currentcollector and facing the electrolyte, a passivation layer. Such apassivation layer refers a material becoming “passive,” that is, lessaffected or corroded by the environment of future use. In addition, orin the alternative, an ion conduction (insulating) or graded interphaselayer can be deposited on layer 412A facing electrolyte 414A to minimizeside reactions with free and/or unattached (physically and/orchemically) Li in ionic form. Prior to the deposition or placement ofany such encasing layer, lithium, in the form of Li ions, may be flowedin liquid state into hierarchical pores 101A and/or 107F of open porousscaffold 102A of any one or more of mesoporous carbon-based particles100A and/or 100E composing layers to form electrochemical gradientsproportionate to the level of concentration of mesoporous carbon-basedparticles 100A and/or 100E composing each layer of layers 406A-412A,layer 406A having the highest concentration of mesoporous carbon-basedparticles 100A and/or 100E permitting for relatively high levels ofelectric current conduction between electrically conductiveinterconnected agglomerations of graphene sheets 101B. Layers 408A-412A(and additional such layers, if necessary or desirable) each haveprogressively lower (sparser) concentration levels of mesoporouscarbon-based particles 100A and/or 100E, thus correspondingly havingproportionately lower levels of electric conductance capabilities.

Repeated (cyclical) li ion electrode usage in secondary batteries canresult in problems due to metal formation, such as volume expansionduring re-depositing in electroplating operations (referring to aprocess that uses an electric current to reduce dissolved metal cationsso that they form a thin coherent metal coating on an electrode). Theterm can also be used for electrical oxidation of anions on to a solidsubstrate, as in the formation of silver chloride on silver wire to makesilver/silver-chloride electrodes. Electroplating is often used tochange the surface properties of an object (such as abrasion and wearresistance, corrosion protection, lubricity, aesthetic qualities), butmay also be used to build up thickness on undersized parts or to formobjects by electroforming.

Processes used in electroplating with relation to infiltration of Li ionsolution into lithiated carbon scaffold 400A may be referred to aselectrodeposition (also known as electrophoretic deposition (EPD)) andis analogous to a concentration cell acting in reverse. Electrophoreticdeposition (EPD), is a term for a broad range of industrial processeswhich includes electrocoating, cathodic electrodeposition, anodicelectrodeposition, and electrophoretic coating, or electrophoreticpainting. A characteristic feature of this process is that colloidalparticles suspended in a liquid medium migrate under the influence of anelectric field (electrophoresis) and are deposited onto an electrode.All colloidal particles that can be used to form stable suspensions andthat can carry a charge can be used in electrophoretic deposition. Thisincludes materials such as polymers, pigments, dyes, ceramics andmetals.

Electroplating, as described above, with Li ions may result in a volumeexpansion on the order of approximately 400% or more of lithiated carbonscaffold 400A. Such an expansion is undesirable from a stabilitystandpoint micro-mechanically and causes degradation with many “deadzones”, referring to inactive or non-chemically and/or electricallyactivated regions, therefore ultimately preventing the derivation oflonger lifespans out of so-equipped Li ion batteries. In any case, it isdesirable to have a majority of the Li ion material plate, meaningreduce onto a smooth and uniform surface to therefore facilitate uniformdeposition of Li ions. Removal will also be smooth in a smooth planarinterface.

Layers 406A-412A, experimentally, have been found (in an example) tohave interfacial surface tension, γ_(sl), engineered to promote wettingof exposed carbon-based surfaces with Li ion. In an example, layer 406Amay be defined as having low-ion transport, high electricalconductivity, low electrical resistance (<1,000 Ω); whereas, layer 412(facing electrolyte 414A) may be defined as having high-ion transport,low electrical conductivity, and high electrical resistance(>1,000−10,000 Ω).

In practice, Li, (when infiltrated into lithiated carbon scaffold 400A)may tend to form unwanted dendrites, defined as crystals that developwith a typical multi-branching tree-like form. Dendritic crystal growthmay be, in certain circumstances, illustrated (in example) by snowflakeformation and frost patterns on a window. Dendritic crystallizationforms a natural fractal pattern. Functionally, dendritic crystals cangrow into a supercooled pure liquid or form from growth instabilitiesthat occur when the growth rate is limited by the rate of diffusion ofsolute atoms to the interface. In the latter case, there must be aconcentration gradient from the supersaturated value in the solution tothe concentration in equilibrium with the crystal at the surface. Anyprotuberance that develops is accompanied by a steeper concentrationgradient at its tip. This increases the diffusion rate to the tip. Inopposition to this is the action of the surface tension tending toflatten the protuberance and setting up a flux of solute atoms from theprotuberance out to the sides. However, overall, the protuberancebecomes amplified. This process occurs again and again until a dendriteis produced.

Such Li ion dendrites (also in the form of acicular Li ion dendrites,“acicular” describing a crystal habit composed of slender, needle-likecrystal deposits) grow away from surfaces upon which Li ions areinfiltrated (such as upon and/or in-between individual graphene sheets101B). In some circumstances, with enough battery charge-dischargecycling, a dendritic protrusion or protuberance will grow across all theway through the cathode and “short” it out, describing when there is alow resistance connection between two conductors that are supplyingelectrical power to a circuit. This may generate an excess of voltagestreaming and cause excessive flow of current in the power source. Theelectricity will flow through a “short” route and cause a “short”circuit.

Employing any one or more of the advanced capillary Li ion infusiontechniques (to be described in further detail herein) into lithiatedcarbon scaffold 400A addresses many of the described shortcomings,inclusive of traditional Li ion battery cathode specific capacity. Anissue encountered in Li ion batteries is that the cathode provides onlya limited quantity of specific capacity or energy capability; moreover,on the anode side, decreases have also been observed in specificcapacity and energy density as well. Thus, even in view of howrelatively desirable (in terms of electric energy storage capacity andcurrent delivery) a Li ion battery may be compared to Li metal hydrideor lead-acid, or Ni Cad batteries (providing energy storage densityfigures a factor of 2-3 greater than any one of those traditionalbattery chemistries), even greater advancements in electric powerstorage and delivery are possible, regarding the protection against orprevention of unwanted Li-based dendritic formations, upon theincorporation of carbon-based materials, such as that disclosed by thepresent examples, and approaches theoretic capacities (not attained inpractice), of pure Li metal, which has a specific capacity of around3,800 mAh/g.

Other approaches have been undertaken including the development ofsolid-state batteries, describing no liquid phases at all. However,attention has returned to Li metal, due to oxide electrolyte being usedto achieve and stabilize contact with Li. And, alternatives to Li metalhave also been explored including Si, Sn and various other alloys.However, even upon elimination of Li metal, a Li ion source may still berequired (as originated from an opposing side of the battery device.)

Alternative-to-lithium materials in a Li ion battery electrode structuremay yield the following energy density values: oxides provide 260 mAh/g;and, sulfur provides 650 mAh/g. Due to its relatively high energydensity capabilities, it is desirable in battery electrode applicationsto confine sulfur (S), so it is not solubilized or dissolved intosurrounding electrolyte. To that effect, sulfur micro-confinement isneeded (as described earlier in relation to pores 105F of open porousscaffold 102A), describing that a “confined” (or “micro-confined”)liquid is a liquid that is subject to geometric constraints on ananoscopic scale so that most molecules are close enough to an interfaceto sense some difference from standard bulk conditions. Typical examplesare liquids in porous media or liquids in solvation shells.

Confinement (and/or micro-confinement, referring to confinement withinmicroscopic-sized regions) regularly prevents crystallization, whichenables liquids to be supercooled below their homogenous nucleationtemperature (even if this is impossible in the bulk state). This holdsin particular for water, which is by far the most studied confinedliquid.

Thus, in view of the various challenges presented above, and others notdiscussed here, various improvements to traditional graphite-basedanodes may be achieved by instead employing few layer graphene (FLG)materials and/or structures, defined as having less than 15 layers ofgraphene grown, deposited or otherwise organized in a stackedarchitecture with Li ions intercalated there-between at defined intervaland/or concentration levels. Any one or more of mesoporous carbon-basedparticle 100A, 100E and/or the like may be so prepared.

Doing so (going from graphite to FLG) may improve specific capacity fromapproximately 380 to over a 1,000 mAh/g for Li-intercalated carbon-basedstructures. Disclosed materials can replace graphite with FLG to permitfor a higher active surface area and can increase spacing in-betweenindividual graphene layers for infiltration of up to 2-3 Li ions, asopposed to just 1 Li ion as commonly may be found elsewhere.

In graphene, hexagonal carbon structures in each graphene sheet may staypositioned on top of each other- this is referred to as an “A-A” packingsequence instead of an “A-B” packing sequence. Particularly,configurations are envisioned for graphene sheets and/or FLG whereindividual layers of graphene may be stacked directly on top of eachother, to obtain incommensurate, disproportionate and/or otherwiseirregular, stacking, which in turn permits for the intercalation ofaddition Li ions in-between each graphene layer of FLG structures.

Under traditional conditions and circumstances, the insertion of Li ionsfrom, the top-down or bottom-up in layered graphene structures may proveexceedingly difficult in practice. Comparably, Li ions more easilyinsert in-between individual graphene layers (separated by a definabledistance). Thus, the key is to manage and tune exactly how much edgearea is available. In that regard, any of the carbon-based structureddisclosed herein are so tunable. And, carbon in graphene is alsoconductive—therefore, this feature provides for dual-roles by: (1)providing structural definition to FLG scaffold electrode structures(such as carbon scaffold 300B and/or lithiated carbon scaffold 400A); (2 ) and, conductive pathways therein.

Production techniques employed to fabricate any one or more of thecarbon-based structures disclosed herein may indicate a desirability ofadjustment of individual graphene-layer edge lengths relative to planarsurfaces thereof; also, the adjustment of the spacing in betweenindividual graphene stacks may be possible. Graphene, given itstwo-dimensional structure, necessarily provides significantly moresurface area in which Li ions can be inserted. Thus, applying graphenesheets in accordance with various aspects of the subject matterdisclosed herein may provide a natural evolution in the direction ofenhanced energy storage density.

Individual graphene sheets are held in position as a part of the plasmagrowth process. Carbon based “gumball-like” structures areself-assembled in-flight (as described earlier) from FLG and/orcombinations of to form particles(such as mesoporous carbon-basedparticle 100A and/or the like) somewhat but with a defined long-rangeorder defined generally and herein as where solid is crystalline if ithas long-range order—once the positions of an atom and its neighbors areknown at one point, the place of each atom is known precisely throughoutthe crystal, to it—smaller structures agglomerate to form essentiallywhat resembles a gumball.

Size dimensions of such “gumball-like” structures (describing individualmesoporous carbon-based particles 100A and/or the like) may be on theorder of 100 nm across (at its widest point). Larger agglomeratedparticles made up from multiple “gumball-like” structures may be anorder of magnitude larger, about 20-30 microns in diameter.

These “gumball-like” structures (individual mesoporous carbon-basedparticles 100A and/or the like) may comprise of multiple FLG structures(electrically conductive interconnected agglomerations of graphenesheets 101B) with Li ions interspersed there-within, at a level of 2-3Liions in-between each individual graphene layer (made possible by thetuning of the height or gap length between individual graphene layers)tied into a carbon scaffold gradient by joining the larger 3Dgraphene-based particles together to form a thin film.

In contrast, traditional battery electrode production methods typicallyemploy known deposition techniques such as chemical vapor deposition(CVD) or other fabrication techniques, nanotubes, etc., to “grow”structures off of a defined fixed substrate or surface. Such knownassembly processes and procedures can tend to be very labor intensive,and they may also permit for the growth of structures of limitedthickness, 200-300 microns in thickness.

Graphene-on-graphene densification, of multiple FLG, on an originalgumball-based carbon scaffold (individual mesoporous carbon-basedparticles 100A, carbon scaffold 300B, lithiated carbon scaffold 400A,and/or the like) may also result in increased energy density andcapacity. Such densification in target regions of the carbon scaffoldmay also be performed or otherwise accomplished after creation of alarger agglomerated particle comprising multiple mesoporous carbon-basedparticles 100A. Generally, Li ions may be plated onto electrode prior toreduction, therefore Li ion may transition from an ion to a metal statedependent on battery chemistry. Moreover, in an implementation, similarto electroplating, graphene may be grown in a stacked manner on othermaterials, such as plastic, and tuned to obtain a desirable brightand/or smooth finish. Such electroplating processes are reversible andmay include separate but interrelated plating process and a strippingprocesses, intended to place the Li ions and/or atoms down (and for thesubsequent removal thereof).

In continual cyclical use of secondary Li ion batteries, involvingmultiple charge-discharge-recharge cycles, surfaces upon whichcarbon-based structures are grown and/or built may eventually roughenedand therefore susceptible to or accommodative of unwanted dendritegrowth. In contrast, techniques employed to produce mesoporouscarbon-based particles 100A and/or the like, as discussed above,substantially prevent such dendrites from growing, enabled by the usageof Li metal substantially free of impurities along with carbon-basedgraphene structures to enable high specific capacity values.

Usage of graphene sheets permits for relatively greater exposed surfacearea available for plating or intercalating operations for theinfiltration (referring to non-reactive capillary infusion) of Li ions.Thus, any tendency to go to a certain point anymore is removed; and,fundamentally the way plating and stripping occurs may be changed (dueto the graphene having a higher surface-area to volume ratio than otherconventional carbon-based materials such as graphite). Li ions may beintroduced at least partially relying upon liquid Li; however, givenLi's predisposition for chemical reactivity with surrounding and/orambient elements, water-based moisture and oxygen must be kept away.Similarly, the introduction of impurities results in deleteriouseffects. Metal-matrix composites have been studied, in relation to thedisclosed carbon-based structures, regarding usage of Li metallicallybonding or otherwise forming a metal-matrix composite with C, thereforeoffering additional options regarding the fine-tunability and managementof reactivity at exposed surfaces.

Li in contact with C may result in circumstances where the free energyof carbide of Li at contact surfaces must be suppressed and/orcontrolled to avoid unwanted reactivity related to spontaneous Liinfiltration in mesoporous carbon-based particle 100A and/or the like.Traditionally, Li, in a liquid phase, typically forms carbonates andother formations due to the chemistry of the electrolyte. However, whatis proposed by the present examples relates to the creation of arelatively stable solid electrolyte interface (SEI) prior to theintroduction of the liquid electrolyte, this is a central conceptsupportive of the surprising performance success of the disclosedexamples and implementations.

Moreover, multiple methods and/or processes to affect Li ion interfaceareas may be available. For instance, preparing the surface of liquid Liby alloying with Si and other elements will reduce the reactivity andpromote overall Li ion wetting of larger agglomerated particles, eachcomprising multiple “gumball” structures (mesoporous carbon-basedparticles 100A). In an example, approximately less than 1.5% of Li wasobserved to have preferentially moved to exposed surfaces, exposed tothe electrolyte.

3D Hierarchical Graphene with Increased Specific Capacity (˜3×) overConventional Graphite Anodes

Commercial use of graphitic carbon materials for anode active materialsas well as fine carbon black materials for electrical conduction isjustified by their relatively low cost, excellent structural integrityfor the insertion and extraction of Li+ions, safety (free from Lidendrite formation), and formation of a protective passivation layeragainst many electrolytes (such as that associated with the formation orbuild-up of the solid electrolyte interphase (SEI)).

The low specific capacity of graphite (at 372 mAh/g, havingstoichiometric formula—LiC₆), however, is a critical limitation and as aresult, can potentially hinder the advance of large-scale energy storagesystems that demand high energy and power densities. By designing andapplying a three-dimensional (3D) graphene (with intercalated Li and/orS compounds) electrode approach, a larger loading amount of active anodematerials can be accommodated while facilitating Li ion diffusion.Further, 3D nanocarbon frameworks (such as that defined by open porousscaffold 102A and/or the like) can impart:

-   -   (1) an electrically conducting pathway; and    -   (2) structural buffer to high-capacity non-carbon nanomaterials,        which results in enhanced Li ion storage capacity.        Both (1) and (2) enhance Li ion storage capacity (>1,000 mAh/g)        and enhanced cycling (stability) performance can be achieved        with these 3D structures.        Integration with Li Ion (and Li S) Battery Electrode

An example Li ion secondary electrochemical cell (battery) system 500 isshown in FIG. 5, having an anode 501 and cathode 502 separated by aseparator 517, all at least partially contained and/or exposed to (Li)ion-conducting electrolyte solution 518 (containing dissociated lithiumion conducting salt 505) as shown. The separator, a porous membrane toelectrically isolate the two electrodes from each other, is also in theposition showed. Single lithium ions migrate through pathway 507 backand forth between the electrodes of the lithium ion-battery duringcharging and discharging and are intercalated into the active materials.

During discharging, when lithium is deintercalated from the negativeelectrode (anode 501 and/or hierarchical mesoporous carbon-based anode503, where copper functions as the current collector), electrons 506 arereleased, for example. The active materials of the positive electrode(cathode 502 and/or hierarchical mesoporous carbon-based cathode 504)are, for example, mixed oxides. Those of the negative electrode mainlyare graphite and amorphous carbon compounds. The positive electrode(cathode 502 and/or hierarchical mesoporous carbon-based cathode 504)contains active materials such as mixed oxides. The active materials ofthe negative electrode (anode 501 and/or hierarchical mesoporouscarbon-based anode 503) mainly are graphite and amorphous carboncompounds. These are the materials into which the lithium isintercalated.

Notably, lithium ion conducting salt 505 (also referring to Li ionsgenerally) can intercalate into any one or more of the uniquecarbon-based structures (referring the mesoporous carbon-based particle100A, 100E, carbon-scaffold 300B, and lithiated carbon-scaffold 400Aand/or the like employed as an anode 503, replacing traditional anode501, and/or a cathode 504, replacing traditional cathode 502) all ofwhich are proprietary to LytEn, Inc., of Sunnyvale, Calif., to achievesurprising and wholly unexpected specific capacity retention capabilityfar in excess of the 372 mAh/g values commonly cited in traditional Liion battery related technologies, inclusive of performance at a level 3×or greater (referring to specific capacity retention capabilitiesexceeding 1,100 mAh/g or more), all made possible through the unique,multi-modal, hierarchical pores 101A and/or 107F defined by open porousscaffold 102A of mesoporous carbon-based particle 100A and/or 100E. Liions form complexes and/or compounds with S, for example, and aretemporarily retained during charge-discharge cycles at levels nototherwise achievable through conventional unorganized carbon structuresrequiring adhesive definition and combination via a binder, which can(as discussed earlier) also inhibit overall battery performance andlongevity.

Lithium ions migrate from the negative electrode (anode 501 and/orhierarchical mesoporous carbon-based anode 503, any one or more of whichfurther include and/or are defined by mesoporous carbon based particles100A and/or 100E with minute carbon particles 509 interspersed therein)through the electrolyte 518 and the separator 517 to the positiveelectrode (cathode 502 and/or hierarchical mesoporous carbon-basedcathode 504, any one or more of which further include and/or are definedby mesoporous carbon based particles 100A and/or 100E with minute carbonparticles 509 interspersed therein) ([using] aluminum as a currentcollector). Here, lithium metal 514 micro-confined (as shown in enlargedareas 516 and 513) within hierarchical mesoporous carbon-based anode 503(and in between graphene sheets 515 associated therewith as shown inarea 513) may dissociate pursuant to the following equation (1):

FLG-Li→FLG+Li+e−   (1)

Eq. (1) shows electrons 511 discharging 508 to power an external loadand lithium ions 512 migrating to cathode 502 and/or hierarchicalmesoporous carbon-based cathode 504 to return to a thermodynamicallyfavored position within a cobalt oxide-based lattice pursuant to thefollowing equation (2):

xLi++xe−+Li_(1-x)CoO₂→LiCoO₂.   (2)

During charging, this process is reversed, where lithium ions 505migrate from the positive electrode through the electrolyte and theseparator to the negative electrode.

Disclosed carbon-based structures (referring to the surprising favorablespecific capacity values made possible by the unique multi-modalhierarchical structures of mesoporous carbon-based particle 100A, 100Eand/or derivatives thereof, including carbon scaffold 300B and lithiatedcarbon scaffold 400A) build upon traditional advantages offered bylithium ion technology. Compared to sodium or potassium ions, the smalllithium ion exhibits a significantly quicker kinetics in the differentoxidic cathode materials. Another difference: as opposed to otheralkaline metals, lithium ions can intercalate and deintercalatereversibly in graphite and silicon. Furthermore, a lithiated graphiteelectrode enables very high cell voltages. Disclosed carbon-basedstructures uniquely and unexpectedly enhance the ease through whichlithium ions can intercalate and deintercalate reversibly betweengraphene sheets, due to the unique lay-out of few-layer graphene (FLG)(5-15 layers of graphene in a generally horizontally stackedconfiguration) 101C as employed in mesoporous carbon-based particle 100Aand/or the like, and are suitable for application in traditionalcylindrical (hardcase), pouch cell (softpack), and prismatic (hardcase)applications.

Stabilization of Artificial Solid-Electrolyte Interface (SEI) Films byDoping

At present, current Li ion batteries (as shown by electrode 600 in FIG.6) form a protective passivation layer, or solid electrolyte interface(SEI), at the electrode surface exposed to electrolyte (generally facingaway from the current collector) during the pre-conditioning step whenthe electrolyte is first introduced followed by initial discharge andcharge steps. Although electrolyte chemistry and pre-conditioningprotocols (charge/discharge rate and overvoltage) may be adjusted tooptimize film passivation (referring to SEI formation), films may stillbe chemically and mechanically unstable.

By introducing (through doping) specific elements 602 (silicon, sulfur,nitrogen, phosphorous) at electrode surface 601 (such as including orotherwise referring to electrodes at least partially created by orincorporating mesoporous carbon-based particle 100A, 100E, carbonscaffold 300B and/or lithiated carbon scaffold 400A, as well asderivates thereof) at specified levels of conformal coverage (such asranging from sparse decoration to complete conformal coverage) duringthe initial electrode fabrication processes (either in the MW plasmaduring innate carbon formation or during pre-lithiation and/orinfiltration, as shown with addition of element 602 additions to thecarbon preform in figure), an artificial solid state electrolyteinterface can be created initially or further stabilized in-situ(referring to on-site or in-position, such as within a reaction chamberor reactor) during pre-conditioning steps of a given battery.

Precedence for formation of stable solid-state ion conducting layershave been reported in literature; referring to sulfide-based thioLISCONs(such as that defined Lithium Sulfur CONductors by the chemical formulaLi_(3.25)Ge_(0.25)P_(0.75)S₄) and phosphate-based NASCIONs (referring tosodium (Na) Super Ionic CONductor, which usually refers to a family ofsolids with the chemical formula Na_(1+x)Zr₂Si_(x)P_(3−x)O₁₂,0<×<3;also, in a broader sense, the acronym is also used for similar compoundswhere Na, Zr and/or Si are replaced by isovalent elements.). In thismanner, the formation of a stabilizing solid state passivation layer (aselucidated by this example of doping specific elements 602 includingsilicon, sulfur, nitrogen, phosphorous at electrode surface 601) can beengineered prior to battery assembly and thereby decouple the formationprocess of a stable solid state ion conducting layer from thereduction/oxidation events that occur when in contact with electrolyte(as encountered in current Li-ion battery fabrication which still oftensuffers from long term stable operation).

Direct “Drop-In” 3D Hierarchical Graphene Particles into ConventionalSlurry Cast Electrode (Manufacturing the Above Using Slurry CastTechniques)

In combination with conductive particles, such as carbon black, andoptionally polymer binders and solvent, such as NMP, tuned 3Dhierarchical graphene particles (referring mesoporous carbon-basedparticles 100A, 100E and/or the like with open porous scaffold 102Adefining hierarchical pores 107F with uniquely sized pores 105F for Smicro-confinement) can be directly incorporated into conventional slurrycast electrode fabrication processes as follows:

-   -   (1) an active graphene based (FLG) substitute for graphite        particles, in the case of the anode;

and/or

-   -   (2) infused with active sulfur (S) in the case of the cathode.        The 3D graphene particles provide high specific capacity        graphene building blocks with interconnected mesoporous ionic        conducting channels for rapid transport along with carbon black        and binder to ensure electrical conducting pathways (referring        to hierarchical pores 107F) and mechanical integrity between        adjacent and/or touching mesoporous carbon-based particles 100A,        100E and/or the like (that may collectively form larger        agglomerations and/or organized structures, such as carbon        scaffold 300B).

Alternatively (or in addition to the above), 3D hierarchical scaffoldparticles (referring to mesoporous carbon-based particles 100A, 100E,carbon scaffold 300B and/or the like) can be pre-lithiated (referring toball milling and/or post thermal annealing and electrochemical reductionfrom a third electrode as discussed earlier), at:

-   -   (1) a relatively low concentration to offset first charge        lithium loss in conventional oxide cathode cell    -   (2) or at a relatively higher concentration to increase overall        specific capacity for both oxide and alternative cathode        configurations, and then slurry cast into electrodes.        For these electrodes, both the electrical conduction and the        concentration of ‘free’ metallic Li can be graded from the        electrolyte-to-electrode to the electrode-to-current collector        interfaces, as shown in the figure, with highest electrical        conductivity and lithium concentration at the current collector        back plane. In addition, an artificial SEI layer can be        incorporated into each of the particles (referring to mesoporous        carbon-based particles 100A, 100E, carbon scaffold 300B and/or        the like) along with Li to facilitate reversible Li ion        conduction and/or transport.

FIGS. 7A-B show various photographs and/or micrographs related ofexample variants (variant 700A and variant 700B) of the 3D mesoporouscarbon-based particles shown in FIGS. 1A-J at various magnificationlevels illustrating internal porosity and microstructure. As can be seenfrom variant 700A, mesoporous carbon-based particle 100A, 100E and/orthe like self-assembles upon an initial nucleation, such as in-flight ina microwave plasma-based reactor (as discussed earlier) to form ornatescaffolded agglomerations such as carbon scaffold 300B suitable forlithiation to become lithiated carbon scaffold 400A.

FIG. 8A shows an enlarged perspective cut-away view of mesoporouscarbon-based particle 100A, 100E and/or the like. Individual ligaments802A formed from as discussed in connection with mesoporous carbon-basedparticle 100A shown in FIG. 1A-F, contact surfaces and/or regionsbetween electrically conductive interconnected agglomerations ofgraphene sheets 101B, may extend to form a lattice and/or tree-likebranched structure of section 800A through which Li ions (Li+) 804A maybe intercalated, inserted in between individual gradient layers ofsection 800A comprising, 3D bundles of graphene sheets 101B . Electriccurrent may be conducted via flow of electrons through contact surfacesand/or regions between interconnected 3D bundles of graphene sheets101B. Ions, e.g., Li ions (Li+), may flow through pores 810A, sized at alarger size of the bi-modal distribution of voids or pores as describedin FIG. 1A-F on the order or 20 to 50 nanometers, or be confined, suchas via chemical micro-confinement, in pores sized generally on the orderof 1 to 3 nanometers.

Therefore, ion flow may be finely controlled or tuned in mesoporouscarbon-based particle 100A to, for example, to be diametrically oppositeto electron flow as needed to facilitate an electrochemical gradientthat may be necessary for electricity conduction and/or electron flowthrough contact points and/or regions of 3D bundles of graphene sheets101B. Spacing between individual carbon-based ligaments may be set a 0.1μm. Those skilled in the art will appreciate that the dimension of 0.1μm is provided as an example only and that other suitable similar ordissimilar dimensions may exist in section 800A of mesoporouscarbon-based particle 100A.

Section 800A may be formed of 3D bundles of graphene sheets 101B thatare sintered together with each other to form a configuration wherethere are no completely open channels such that electricity isnecessarily conducted through contact points and/or regions ofinterconnected 3D bundles of graphene sheets 101B. Thus, liquid passingthrough voids 804A and the conductive nature of carbon-to-carbon bondingfacilitates a connection of carbon-based materials to other carbon-basedmaterials without the necessity of a chemical binder and/or chemicalbinding material or agent, many of which resulting in undesirablechemistries or side effects regarding functionality of mesoporouscarbon-based particle 100A.

Open porous scaffold 102A of mesoporous carbon-based particle 100Apresents a departure from traditional industry-standard batteryelectrodes that may involve slurry-cast “boulders”, relatively largeparticles, organized haphazardly on a substrate, such boulders typicallyrequiring a binder to be held together to conduct electricitythere-through. Open porous scaffold 102A defined by hierarchical pores101A and/or 107F of mesoporous carbon-based particle 100A allows forimproved electrical conduction therein.

FIG. 8B shows the mesoporous carbon-based particle of FIG. 8A withgraphene-on-graphene densification. For the example of FIG. 8B, surfaces800B shown in FIG. 8B and/or surfaces 808A shown in FIG. 8A at edgeregions, at least partially planar surfaces of the branched, tree-likestructure of section 800A of mesoporous carbon-based particle 100A, maybe densified upon the application, deposition, or otherwise growth ofmultiple additional graphene layers. Such densification processes,methods and/or procedures permit for the creation of intricate,multi-layer, and potentially nearly infinitely tunable 3D carbonstructures comprising combinations of 3D bundles of graphene sheets101B. Accordingly, such fine tunability accomplished bygraphene-on-graphene densification may facilitate the attainment ofparticular electrical conductivity values when mesoporous carbon-basedparticle 100 is integrated into an electrode of a battery.

FIG. 9A shows various images of carbon and/or graphene and carbonparticle-based 3D structures with high degrees of purity and tunability.In the example of FIG. 9, a first example carbon-based 3D structure 900Ais shown having a dimension on the scale of 10 nm. Such a dimension isprovided as an example. Particular plasma-based processing conditions,as applied or performed in a reactor such as a thermal reactor, forexample, may be adjusted to with a high degree of tunability to achievestructures 902A and/or 904A, (as well as carbon nano-onions, CNOs, asshown in micrograph 100H in FIG. 1H, which can be produced in a thermalreactor and be used in batteries, CNO structures often consuming up toapproximately 30% of a given cell electrode by volume) andgraphene-on-graphene densification processes may be employed to grow orotherwise create complex 3D structures such as structure 906A. FIGS.9B-9E illustrate micrographs (900B, 900C, 900D and/or 900E) of variousexample carbon-based materials such as variants of mesoporouscarbon-based particle 100A, 100E and/or the like at variousmagnification levels.

FIG. 10A shows a planning diagram representative of traditionalsilicon-chip based manufacturing techniques and related information. Inthe example of FIG. 10A, object 1000A describes various items associatedwith traditional silicon-based computer microchip manufacturing andprocessing, including usage of silane 1002A (SiH₄) as a precursor toelemental silicon, applied in clean room type facilities 1004A, wheresilicon wafers 1006A may be diced to produce individual silicon-basedmicrochips 1008A requiring the burning and/or release of hydrogen gas(H₂) emitted as an exhaust. Such manufacturing techniques may beemployed by various high-technology related industries 1010A such ascomputing, networking, electronic and/or power devices, and many others,any one or more of which being substantially capital expenditure(“CAPEX”) heavy, being required to be performed at artificiallycontrolled sub-atmospheric clean-room based conditions.

FIG. 10B shows a planning diagram representative of advanced 3D grapheneand/or carbon-based industry-focused applications and/or solutions. Inthe example of FIG. 10B, and in contrast to object 1000A depicting thatassociated with traditional silicon-based computing microchipmanufacturing processes, object 1000B depicts advanced, carbon-based,sustainable manufacturing techniques for various end-use industrialapplications, such as those relying upon supply of methane 1002B (CH₄)gas as a suitable precursor for single-layer graphene synthesis. Sourcegases, plasmas, and/or other feedstock materials may be supplied tofacilitate gas phase nucleation innately in specially prepared and/orconventional reactors 1004B to create advanced carbon-based structuresand/or materials, such as those described in mesoporous carbon-basedparticle 100A shown in FIGS. 1A-1F. Additionally, or alternatively,carbon-based materials may be fused, reacted and/or otherwise combinedwith metals and/or metallic materials to produce covetic materialsand/or structures 1006B, where any emitted hydrogen gas (H₂) may berecaptured by processes 1008B so directed for subsequent usage in powergeneration and/or transport fuels. Such capabilities made possible bythe manufacture and implementation of advanced carbon-based materialsfacilitate disruptive performance improvements 1010B in a variety ofend-used applications and industries, including (but not limited to):batteries, printable computing, composites, tires, etc. Any one of moreof such end use applications may not require the usage of dedicatedclean-room type facilities, therefore ultimately reducing overallcapital expenditure 1012B.

FIG. 11 shows micrographs 1100 of 3D multi-shell fullerenenano-capacitors (such as those in the form of carbon nano-onions, CNOs,which may be derived from similar or identical synthetic procedures asmesoporous carbon-based particle 100A and/or the like to yield similarsurprising and beneficial properties useful in battery electrode end-useapplications). In the examples of FIG. 11, innate graphene properties,that may be variable according to process conditions, etc., are shown assupporting electro-active to structurally demanding materialapplications in images 1102, 1104. Image 1102 depicts 3D multi-shellfullerene nano-capacitors, which may be prepared to store and/or supplyelectric charge and/or current at the 10 nm scale. Holes, openingsand/or orifices can be created by penetrating CNOs and relatedstructures to receive active material, such as lithium, cobalt,manganese (spinel), NCM (nickel-cobalt manganese), and phosphate, whichmay be inserted and retained in the holes. Image 1104 shows 3D few-layergraphene (“FLG”), structural FLG at the 50 nm scale.

FIG. 12 shows a listing of properties associated with example 3Dgraphene-based scaffolded particles (such as mesoporous particle 100Aand carbon scaffold 300B). In the example of FIG. 12, listing 1200describes various example parameters and/or physical properties of 3Dscaffolded particles. Sample parameters and/or physical properties of 3Dscaffolded particles disclosed herein, including mesoporous carbon-basedparticle 100A shown in FIGS. 1A-1F, including employing fabricationand/or construction techniques relating to tunable hierarchical pores,tuning regarding both size, and distribution thereof in the 1-2 nm microscale to >40 nm meso scale sized pores.

Nanoscale sized tuning may be performed on 3D scaffolded particles toopen 3D channels to create and/or form building blocks within a micronscale or at a larger, macro-particle, sized scale. Surface chemistriesused to prepare and/or synthesize 3D scaffolded particles may betunable, by using, as feedstock, materials including pristine to dopedgraphene. Other areas may be tuned as well including adjustment ofparameters used to create 3D scaffolded particles to achieve particularenumerated mechanical integrity and/or strength goals by tuning ofcarbon-based connecting ligaments. Any one or more of the discussedtuning mechanisms may be accomplished, for example, to achieveparticular enumerated mechanical integrity/strength objectives, byadjustment of ligaments. Any one or more of the discussed tuningcapabilities, and others, may be accomplished at a relatively low cost,both in terms of capital investment and ongoing operations, tofacilitate convenient high-volume carbon production.

FIG. 13 shows various charts, equipment, and particle products of carbonand/or 3D graphene. In the example of FIG. 13, plasma-based processesconducted within a reactor 1302, such as a thermal reactor, may be tunedbetween various plasma modes and/or conditions 1300 to achieve a finalend-use and/or application particle product 1304, shown here in particleand/or particulate form.

FIG. 14 shows various depictions 1400 of porous innately graphenenano-platelets (“GNP”) connected particle products (such as thosederived from mesoporous particle 100A and carbon scaffold 300B) and/orFLG and related equipment. In the example of FIG. 14, a schematic of amesoporous carbon-based particle and/or scaffolded structure 1402 isshown as representative of particle product 1404. Scaffolded structure1402 is shown depicted in various images showing: nodules (particleproduct 1404), generally known regarding in chemistry and composites asan aggregation or lump of matter distinct from its surroundings; FLG1406, defined herein and understood to refer to <10 layers of graphenegenerally configured in a stacked orientation; surface etching 1408 ofcarbon-based particles showing tunable spacing 1412, as well as dopedsurfaces 1414. Further, energy optimized non-equilibrium plasmaprocessing 1410 may be used to fine tune carbon scaffold and/orscaffolded structure 1402 generate to achieve desirable end-useapplication physical parameter goals.

FIG. 15 shows a schematic depiction 1500 of a 3D graphene-particlecathode scaffold (such as carbon scaffold 300B) featuring sulfur (S)micro-confinement therein. In the example of FIG. 15, graphene-basedsheets and/or structures containing sulfur entrainment and/orconfinement 1502 in various 3D cathode scaffolded structures orconfigurations, of various thicknesses 1504 and 1506, are shown. Sinclusion in graphene-based battery chemistry provides desirableelectric charge storage and retention (measured in milliamp hours),further described by the synthesis of a graphene-sulfur compositematerial by wrapping poly(ethylene glycol) (PEG) coated submicrometersulfur particles with mildly oxidized graphene oxide sheets decorated bycarbon black nanoparticles.

The PEG and graphene coating layers are important to accommodatingvolume expansion of the coated sulfur particles during discharge,trapping soluble polysulfide intermediates, and rendering the sulfurparticles electrically conducting. The resulting graphene-sulfurcomposite showed high and stable specific capacities up to ˜600 mAh/gover more than 100 cycles, representing a promising cathode material forrechargeable Li batteries with high energy density. Other studies haveshown that activated graphene (AG) with various specific surface areas,pore volumes, and average pore sizes [have been] fabricated and appliedas a matrix for sulfur. The impacts of the AG pore structure parametersand sulfur loadings on the electrochemical performance of Li -sulfurbatteries are systematically investigated.

The results show that specific capacity, cycling performance, andCoulombic efficiency of the batteries are closely linked to the porestructure and sulfur loading. An AG3-sized (S) composite electrode witha high sulfur loading of 72 wt. % exhibited an excellent long-termcycling stability (50% capacity retention over 1,000 cycles) andextra-low capacity fade rate (0.05% per cycle). In addition, when LiNO₃was used as an electrolyte additive, the AG3/S electrode exhibited asimilar capacity retention and high Coulombic efficiency (−98%) over1000 cycles. The excellent electrochemical performance of the series ofAG3/S electrodes is attributed to the mixed micro/mesoporous structure,high surface area, and good electrical conductivity of the AG matricesand the well-distributed sulfur within the micro/mesopores, which isbeneficial for electrical and ionic transfer during cycling.

FIG. 16 shows a 3D few-layer graphene anode scaffold (such as carbonscaffold 300 and/or lithiated carbon scaffold 400A) with Liintercalation between graphene layers. In the example of FIG. 16, Liions (Li+) are shown in various configurations 1600 including as beingintercalated into FLG 1602 and reversible inclusion of Li metal in acarbon-based host scaffold 1604. Lithium intercalation into bilayergraphene may relate to the real capacity of graphene and thelithium-storage process in graphite, which present problems in the fieldof lithium ion batteries.

Corroborated by theoretical calculations, various physiochemicalcharacterizations of the staged lithium bilayer graphene productsfurther reveal the regular lithium-intercalation phenomena and thereforefully illustrate this elementary lithium storage pattern oftwo-dimension. These findings not only make the commercial graphite thefirst electrode with clear lithium-storage process, but also guide thedevelopment of graphene materials in lithium ion batteries.

Li absorption and intercalation in single layer graphene and few layergraphene differs to that associated with bulk graphite. For single layergraphene, the cluster expansion method is used to systemically searchfor the lowest energy ionic configuration as a function of absorbed Licontent. It is predicted that there exists no Li arrangement thatstabilizes Li absorption on the surface of single layer graphene unlessthat surface includes defects. From this result follows that defect poorsingle layer graphene exhibits significantly inferior capacity comparedto bulk graphite.

FIG. 17 shows a listing of properties and/or features associated withintegrated 3D scaffolded films. In the example of FIG. 17, integratedmesoporous carbon-based particle films 1700 include at least thefollowing particle-like properties, in addition to:

-   -   (1) sacrificial, as well as, supporting film substrate;    -   (2) tunable velocity to substrate;    -   (3) tunable impact energy from implantation to adsorption;    -   (4) tunable thickness; and,    -   (5) tunable porosity; any one or more of which can be integrated        with additive type manufacturing capability.

FIG. 18 shows a listing of properties and/or features associated with areactor to film processed carbons. In the example of FIG. 18, carbonsmay be processed from a reactor to a film state via at least thefollowing processes 1800: roll to roll processing; covalently bondedcarbon rich electrode interfacing; and, cathode and anodes depositionwithout the heavy use of inactive binders.

FIG. 19 shows a general progression 1900 of proprietary carbondeposition on film processes integrated with roll-to-roll processing. Inthe example of FIG. 19, proprietary covalently bonded carbon-richelectrode interfaces 1902 may be created through proprietary depositionprocesses, those provided by LytEn, Inc., of Sunnyvale, Calif.,including roll-to-roll synthesized carbon to carbon processes to createtuned carbon coatings 1904 and coated materials 1906 in-linefacilitating further functionalization and synthesis. Coated materials1906 may be prepared to accommodate any one or more offunctionalization, sulfidation, lithiation, and/or the like.

Efforts have been undertaken in the roll-to-roll processing ormanufacturing areas, as further elucidated by the “Roll to Roll (R2R)Processing Technology Assessment”, supported at least in part by theU.S. Dept. of Energy, which states that “[r]oll-to-roll (R2R) is afamily of manufacturing techniques involving continuous processing of aflexible substrate as it is transferred between two moving rolls ofmaterial.

R2R is an important class of substrate-based manufacturing processes inwhich additive and subtractive processes can be used to build structuresin a continuous manner. Other methods include sheet to sheet, sheets onshuttle, and roll to sheet; much of the technology potential describedin this R2R Technology Assessment conveys to these associated,substrate-based manufacturing methods.

R2R is a “process” comprising many technologies that, when combined, canproduce rolls of finished material in an efficient and cost-effectivemanner with the benefits of high production rates and in massquantities. High throughput and low cost are the factors thatdifferentiate R2R manufacturing from conventional manufacturing which isslower and higher cost due to the multiple steps involved, for instance,in batch processing. Initial capital costs can be high to set up such asystem; however, these costs can often be recovered through economy ofscale. FIG. 1 illustrates an example of R2R processing of astate-of-the-art nanomaterial used in flexible touchscreen displays.

FIG. 20 shows a listing 2000 of proprietary engineered 3D carbons thatenable significant battery performance advantages over currentlyavailable Li -ion batteries. In the example of FIG. 20, any one or moreof mesoporous carbon-based particle 100, shown in FIG. 1, and/or 3Dbundles of graphene sheets 102 and/or conductive carbon particles 104may be organized within mesoporous carbon-based particle 100 during itsconstruction and/or creation to achieve any one or more of the physicaland/or electrical energy storage and/or conductivity values recited inFIG. 15, such as (but not limited to): 400 to 650 (W·h)/kg, with amaximum theoretical value of 850 (W·h)/kg, and also including aspectswith a sulfur and/or sulfur-intercalated cathode of 650 (MAh)/ g, and,aspects of 3D bundles of graphene sheets 102 and/or conductive carbonparticles 104 interspersed therewith to define pores and/or voids, etc.,as substantially discussed in connection with that shown in FIG. 1, withionic Li (Li+) intercalated therewith, achieving energy density storagevalue of 900 to 2,000 (mAh)/g.

FIG. 21 shows various images 2100 of a sulfur cathode and a Li-S systemperformance chart over cycles. In the example of FIG. 21, example Li-sulfur batteries having electrodes created with graphene sheets 101Band/or mesoporous carbon-based particle 100A, both shown in FIGS. 1A-1F,are tested. Li -sulfur batteries have a high specific energy ceiling(>2.6 kWh/kg theoretical and ˜840 W·h/kg practical) and are showndeteriorating over repeated usage cycles, in images 2102 showing Cycle0-Cycle 100, such deterioration having a measurable impact on percentagecapacity retention performance in Li-S systems, as shown by graph 2104.Common challenges associated with such Li-S batteries include thatpolysulfide shuttling causes a large capacity drop between cycles 0-3,and a loss of sulfur into the electrolyte; constant degradation overcycles 3-100 as caused by consumption of sulfur by anode materials; and,studies have shown that even industry state-of-the-art cathodes haveaveraged reliable performance metric figures over ˜100 stable cycles dueto complicated failure mechanisms.

FIG. 22 shows cathode specific capacity levels over cycles and variousrepresentative sulfur-nano confinement (as representative of applicationand/or usage of systems based on or using mesoporous carbon-basedparticle 100A and derivatives thereof) diagrams and images. In theexample of FIG. 22, various imagery 2200 is shown concerning depictionsof sulfur nano-confinement in graphene layers 2202 as well as imagesthereof 2204 and with a sulfur map 2206. Improved cathode specificcapacity, electrode level, as measured in mAh/g, is shown in graph 2208for various compositions and/or compounds, any one or more of which atleast partially include mesoporous carbon-based particle 100A formedwith sulfur integrated therewith to enhance cathode specific capacity.

FIG. 23 shows various images, tables and charts (including optical cellanalyses 2302 and 2304) regarding accelerated carbon tuning to mitigatepolysulfide related issues. In the example of FIG. 23, imagery 2300 isshown regarding the effects observed of changing carbon properties onpolysulfide shuttling, indicating overall that increasing the porosityof carbon-based materials, mesoporous carbon-based particle 100A andvariations thereof, reduces polysulfide shuttling, defined as “wheresulfur species reach the negative electrode surface and undergo chemicalreduction”, shown in optical cell analyses 2302 and 2304. Table 2306indicates values of relatively low porosity mesoporous carbon-basedparticle materials having a shuttling current of 6.15 mAh/g_(s), and ofrelatively high porosity mesoporous carbon-based particle ed materialshaving a shuttling current of 4.22 mAh/g_(s). Chart 2308 shows a meanintensity change of low porosity carbon generally at higher levels thanhigh porosity carbon. Chart 2310 shows high porosity carbon generallywith higher levels of percentage capacity retention over repeatedbattery usage cycles relative to low porosity carbon.

FIG. 24 shows proprietary 3D graphene and 3D graphene-based particles inrelation to sulfur infusion and its relation to battery capacity andstability. In the example of FIG. 24, chart 2400 shows currentprocesses, referring to those substantially with implementation ofmesoporous carbon-based particle 100A and/or the like, shown in FIGS.1A-F, with the electrodes of a Li -ion battery to improve performancethereof, as showing better percentage capacity retention than earlier,“Genl-Process”, processes.

FIG. 25 shows micrographs 2500 revealing uniform distribution of sulfurin a microporous carbon, such as through various images, includingfalse-color images produces for the purposes of visual differentiationand clarity, revealing a relatively uniform distribution of sulfur in amicroporous carbon.

FIG. 26 shows a chart for specific capacity (mAh/g) vs. percentage ofsulfur (thermo-gravimetric analysis value; TGA). In the example of FIG.26, chart 2600 shows increasing values of specific capacity forreplicate, substantially similar, batches of carbon-based materials,mesoporous carbon-based particle 100A as shown in FIGS. 1A-F, forincreasing values of sulfur entrainment there-within. Chart 2600 shows agenerally positive trend for specific capacity retention proportionateto increasing sulfur values.

FIG. 27 shows a graph of percentage battery electric storage capacityretention over cycles. In the example of FIG. 27, chart 2700 showscapacity retention for various battery and/or battery electrodes atleast partially equipped with mesoporous carbon-based particle 100A invarious forms per cycle number, referring to charge-discharge cycles.

FIG. 28 shows a listing of various battery-related industry challenges.In the example of FIG. 28, listing 2800 indicates various batteryindustry related challenges, including (but not limited to): undesirabledendrite growth, describing a characteristic tree-like structure ofcrystals growing as molten metal solidifies, the shape produced byfaster growth along energetically favorable crystallographic directions,and also having significant consequences in regard to materialproperties, due to the presence of Li -related compounds; control offirst charge Li loss (balance of pre Li loading); and, continuous growthof solid-electrolyte interphase (“SEI”) on fresh Li surfaces.

FIG. 29A shows a proprietary approach 2900A of a pre-lithiated carbonhost structure. In the example of FIG. 29A, methods and/or processesconducted by LytEn, Inc., of Sunnyvale, CA, may at least partiallyemploy a “pre-lithiated” configuration, referring to carbon hoststructure surfaces, such as mesoporous carbon-based particle 100A shownin FIGS. 1A-1F, prepared for the acceptance of Li ions (Li+)intercalated therewith, such a configuration permitting for: tuning ofgraphene inter-layer spacing and pore distribution (size and volume)within a plasma-based thermal reactor; formulation of a carbon-basedhost structure; accommodation of Li intercalation into graphene (2-3×specific capacity over currently available materials); and, creation ofartificial solid state SEI during Li infiltration processes.

FIG. 29B shows listing 2900B that includes plans for battery anodedevelopment concerning pre-lithiation preparation thereof; notably, Limetal and/or ions are identified as being desirable for inclusion withina battery, Li -ion battery anode, but undesirable and/or unpredictabledendrite growth and/or formation due to, for example, unstable SEIformation and infinite relative dimensional change limit potentialapplication areas. A key challenge of a need to stabilize Li metaland/or liquid electrolyte at their interface areas and/or regions may beand/or need to be further identified.

Various mitigating approaches shown in listing 2900C, alternatives to anideal, pure Li and/or Li ion intercalation with graphene-based sheets(such as those used to form or produce 3D bundles of graphene sheets 102of mesoporous carbon-based particle 100) have been considered to addvalue to Li -ion battery electrodes. Traditional, state-of-the-artbattery systems may, for example, replace Li metal with intercalatingcarbon (graphite) and/or use Li sourced from an oxide cathode to producea battery. Further, include mesoporous carbon-based particle 100 may becreated with alloys or alternative active materials to Li, silicon, tinaluminum, and/or the like.

Pre-lithiation procedures, defined as those including the intercalationof graphite to accommodate initial charge Li loss and/or to provide anactive source for electric charge storage or current flow may includeadjustments and/or optimizations to any one or more of the followingproperties and/or parameters: chemical, electrochemical, and/oremploying deposition or fabrication techniques to ensure direct contactof carbon-based materials in mesoporous carbon-based particle 100A to Limetal, provided by FMC and/or Livent Corp., of Philadelphia, Pa., infoil, powder, or other forms.

Adjustments made to the percentage lithiation shown in listing 2900D, Liintercalation between graphene sheets of 3D bundles of graphene sheets101B, may, for example: increase coulombic efficiency, decrease firstcharge loss, manage expansion effects, and engineer solid electrodeinterphase (“SEI”) in conventional graphite electrodes; provide dualpurpose, serve as a cranking battery and power a trolling motor inmarine applications, in Li ion capacitors; guard against excessivefreely-accessible (“free”) Li, that can lead to high surface area Liformation; and, enable alternative non- Li cathodes such as sulfur,oxygen, vanadium oxide, etc.

Tuning of mesoporous carbon-based particle 100A may achieve, generally,at least the following shown in listing 2900E of FIG. 29E: moreefficient fabrication (Li utilization and potential increase in activeto inactive, binder reduction); improved uniformity; and, controlledreaction (battery electricity conductivity and/or activity). Moreparticularly, parameters of mesoporous carbon-based particle 100A may betuned to achieve specific performance features as a function of thepercentage of Li loading per unit area or volume of mesoporouscarbon-based particle 100A, including (but not limited to):

-   -   (1) at low loading levels (less than capacity), compensating for        first charge losses/more effective SEI formation; at        saturation/matched loading, Li rich regions, ‘galvanically’        coupled to carbon,    -   (2) oxidizing materials when in contact with electrolyte and        insertion of Li and/or Li -ions (via intercalation) between        graphene layers;    -   (3) at excess loading levels, metallic Li is infiltrated into        engineered “host” carbon;

configuring the “host” to serves to accommodate/stabilize expansion ofLi and suppress dendrite formation as a result of increased Li surfacearea (enables specific capacities commensurate with pure Li: >2,000mAh/g); and,

-   -   (4) preparing Li ion processes/methodology directly transferable        to lithium ion hybrid capacitors.

Ongoing challenges, shown in FIG. 29F, related to the thermal and/orliquid infusion of Li and/or Li ion into carbon-based structures such asmesoporous carbon-based particle 100A as outlined in listing 2900E mayinclude that set forth in listing 2900F, such as (but not limited to):management of Li reactivity regarding surface tension, wettability) atinterface; management of capillary infiltration kinetics; engineering ofelectrical gradient through electrode thickness, gradation of Liinfiltration such that it is highest at current collector andtransitions to a more ionic conducting concentration and/or level atelectrolyte interface; and, the carefully tuned engineering of surfacechemistry (by facilitating stable SEI formation in contact withelectrolyte and minimize reactivity with air).

Disclosed aspects may build upon traditional two-dimensional (“2D”)plating, that may be similar to brightening agents in electroplating.Listing 2900G shown in FIG. 29G outlines that, in electroplating, theaddition of chemical additives may often increase polarization, decreasecurrent density; such as, redirect current density to low as opposed tohigh areas (protrusions); produce a relatively high nucleation rate, andresult in a moderate charge transfer rate. In the context of plating orstripping for battery charge and discharge cycles, for batteries withelectrodes equipped with mesoporous carbon-based particle 100A as shownin FIG. 1, carbon film may serve as a flexible support for SEI formationas well as, redirecting current density to low, as opposed to high,areas.

FIG. 29H shows a schematic depiction of interlayers of material involvedin traditional electroplating processes, where surface curvature valuesfor such processes may be too substantial for effective electroplatingto occur.

FIG. 291 shows a schematic depiction of various carbon spheres formed oncopper (Cu) with one or more layers of Li ions (Li+) depositedthere-upon for the purposes of enhancement of electrical charge storageand current conductivity therefrom.

FIG. 29J shows listing 2900J setting forth various benefits associatedwith the integration of mesoporous carbon-based particle 100A with 3Delectrodes of Li -ion batteries, including, for example: the developmentand implementation of 3D electrodes with increased electroactive surfacearea (such as 3D “host” structures prepared specifically for theintercalation of Li ions therewith, or other metallic materials, for thepurposes of facilitating electric current conductance) that can alsoreduce local effective current density; formation of insulating(wettable polar surface) layer on electrolyte-facing surfaces ofelectrodes with electrical conductivity being graded higher to activecarbon core and backplane current collectors.

FIG. 29L shows listing 2900L setting forth Li ion battery relatedtechnologies that may be equipped with mesoporous carbon-based particle100A and variants thereof as disclosed herein. Galvanic corrosion orcoupling, referring to an electrochemical process in which one metalcorrodes preferentially when it is in electrical contact with another,in the presence of an electrolyte, may be prevalent upon directelectrical contact between carbon and Li metal in the presence ofelectrolyte. The potential difference between Li metal (−3.04 V vs. astandard hydrogen electrode “SHE”), and carbon electrode may lead to aflow of electrons (galvanic couple), formation of Li ions (oxidation),and deposition on carbon and/or carbon-based materials.

Employed herein in a context of producing mesoporous carbon-basedparticle 100 and integrating it with a Li ion battery, classiccementation, referring to a process of altering a metal by heating it incontact with a powdered solid, precipitation in copper production mayrefer to and/or involve a heterogeneous process. Such a process mayimply conditions where reactants are components of two or more phases(solid and gas, solid and liquid, two immiscible liquids) or in whichone or more reactants undergo chemical change at an interface, on thesurface of a solid catalyst, in which ions are reduced to zero valenceat a solid metal surface (i.e., Cu ions on Fe particle surface); and,where iron oxidizes and copper is reduced (copper being relativelyhigher on a galvanic series, similar to Li versus C).

FIG. 29M shows listing 2900M setting forth capabilities of mesoporouscarbon-based particle 100A being prepared for the infiltration of Li ioninto carbon-based materials followed by cementation therewith, as sodescribed by listing 2900L in FIG. 29L, in the presence of anelectrolyte.

FIG. 29N shows listing 2900N that discusses management of reactivemetals from a welding perspective, and that any one or more of thementioned techniques and/or processes may be functionally integratedwith and/or used to produce mesoporous carbon-based particle 100A toenhance Li ion battery performance. Such ancillary processes and/ortechniques include: management of reactive metals (via welding); classicmetal inert gas (MIG), gas tungsten arc welding (GTAW) also referred toas tungsten inert gas (TIG) and submerged arc welding (SAW) to utilizeinert shielding gas to join reactive metals (such as Ti and Al) througha liquid metal process (such as by welding). Examples include usinginert shielding gas to form liquid pools of reactive metal withoutoxidation, where delta Gf of oxides (TiO₂, A12O₃) is on par with that ofLi₂O.Through controlled use of inert shielding gas around reactivemetals, oxygen and moisture may effectively be managed in the presenceof reactive liquid metals. In such environments and conditions, liquidLi can be infiltrated into the carbon-based structures of mesoporouscarbon-based particle 100 through controlled shielding gas configurationand operation.

FIG. 30 shows Raman spectra for 3D N-doped FL graphene includingcharting for both pristine carbon and N-dope carbon. In the example ofFIG. 30, Raman spectra for 3D N-doped FL graphene 3000 includes 2D peak3002 at approximately 2730 cm-1 and D peaks 3004, 3006 at approximately1600 cm⁻¹ and 1400 cm⁻¹, respectively.

FIG. 31 shows a listing of reactor tuning. In the example of FIG. 31,reactor tuning 3100 may be performed to, for example: increase FLgraphene spacing, reduce Van der Waal forces; control doping; promotecarbon vacancy formation; and, decreases Li adsorption energy and/orincrease Li capacity. Li ion intercalation may, for example, shiftgraphene sheet stacks from an “AB” configuration to “AA” withintercalation (increased spacing), where, for example, in graphite, AAmay shift back to AB with de-intercalation; and, in FL graphene, in FLgraphene, AA stacking remains with de-intercalation (maintains increasedspacing). Such stacking configurations may be associated with mesoporouscarbon-based particle 100 shown in FIG. 1.

FIG. 32 shows various properties associated with bilayer graphene 3200.In the example of FIG. 32, a sample bilayer graphene infrastructure 4100is shown with two layers of graphene oriented in the position shown,understood as devices “which contained just one, two, or three atomiclayers”. Schematic 3202 shows approximate spacing measurements of 1.42Å, 1.94 Å and/or 3.35 Å between individual graphene sheets. Schematic3204 shows various example defective sites 3206 and/or 3208 what mayoccur within a defined vicinity of an edge plane and/or assist with thecreation of mesoporous carbon-based particle structures including one ormore graphene sheets. Schematic 3210 shows various model diagrams 3212of a top view of a hard-sphere carbon-particle model.

FIG. 33 shows an illustrative flowchart for depicting an exampleoperation 3300for preparing a 3D scaffolded film containing carbon-basedparticles. In the example of FIG. 33, method 4400 includes preparing athree-dimensional (“3D”) scaffolded film containing carbon-basedparticles therein at operation 3304 by providing the 3D scaffolded filmto a roll-to-roll processing device or apparatus at operation 3306.Carbon rich electrodes may be deposited on the 3D scaffolded film atoperation 3308; and, processing the 3D scaffolded film on theroll-to-roll processing device or apparatus independent of applicationof chemically inactive binding materials may occur at operation 3310prior to conclusion of the method 3300 at operation 3312.

In the foregoing specification, the disclosure has been described withreference to specific examples. It will however be evident that variousmodifications and changes may be made thereto without departing from thebroader spirit and scope of the disclosure. For example, theabove-described process flows are described with reference to aparticular ordering of process actions. However, the ordering of many ofthe described process actions may be changed without affecting the scopeor operation of the disclosure. The specification and drawings are to beregarded in an illustrative sense rather than in a restrictive sense.

1. A composition of matter nucleated from a homogenous nucleation andforming a self-assembled binder-less mesoporous carbon-based particle,the composition of matter comprising: a plurality of electricallyconductive three-dimensional (3D) aggregates formed of graphene sheetsand sintered together to define a 3D hierarchical open porous structurecomprising mesoscale structuring in combination with micron-scalefractal structuring and configured to provide an electrical conductionbetween contact points of the graphene sheets; and a porous arrangementformed in the 3D hierarchical open porous structure and arranged tocontain a liquid electrolyte configured to provide ion transport througha plurality of interconnected porous channels in the 3D hierarchicalopen porous structure, a respective porous channel of the plurality ofporous channels comprising: a first portion configured to providetunable ion conduits; a second portion configured to facilitate rapidion transport; and a third portion configured to at least partially ortemporarily confine active material.
 2. The composition of matter ofclaim 1, wherein the mesoporous carbon-based particle is configured tobe grown at least in part by a vapor flow stream.
 3. The composition ofmatter of claim 2, wherein the vapor flow stream is configured to beflowed at least in part into a vicinity of a plasma.
 4. The compositionof matter of claim 2, wherein the vapor flow stream is flowed at apressure range between a vacuum and substantially atmospheric pressure.5. The composition of matter of claim 2, wherein the mesoporouscarbon-based particle is configured to be grown from a carbon-basedspecies.
 6. The composition of matter of claim 5, wherein thecarbon-based species is configured to be controlled gas-solid reactionsunder non-equilibrium conditions.
 7. The composition of matter of claim1, wherein the graphene sheets define Li containing structuresconfigured to provide a source for specific capacity of an anode orcathode at a range of between approximately 744 mAh/g and approximately1,116 mAh/g.
 8. The composition of matter of claim 6, wherein thegas-solid reactions are affected at least in part by any one or more of:ionization potentials and/or thermal energy associated with constituentsof the carbon-based species; and kinetic momentum associated with thegas-solid reactions.
 9. The composition of matter of claim 1, wherein Liis configured to infiltrate and react with the 3D hierarchical openporous structure.
 10. The composition of matter of claim 1, wherein thetunable ion conduits are configured for ion transport.
 11. Thecomposition of matter of claim 1, wherein the graphene sheets compriseone or more of single layer graphene (SLG), few layer graphene (FLG), ormany layer graphene (MLG).
 12. The composition of matter of claim 11,wherein the FLG includes between approximately 2 and 15 layers ofgraphene.
 13. The composition of matter of claim 12, wherein the layersof graphene are configured to be oriented in a stacked configuration.14. The composition of matter of claim 1, wherein the first portion hasat least one dimension of approximately >50 nanometers.
 15. Thecomposition of matter of claim 1, wherein the second portion has atleast one dimension of in a range of approximately 20 nanometers toapproximately 50 nanometers.
 16. The composition of matter of claim 1,wherein the third portion has at least one dimension less thanapproximately 4 nanometers.
 17. The composition of matter of claim 1,wherein one or more material properties of the mesoporous carbon-basedparticle are configured to be defined during its synthesis.
 18. Thecomposition of matter of claim 1, wherein one or more dopants areincorporated into the mesoporous carbon-based particle.
 19. Thecomposition of matter of claim 18, wherein the one or more dopants areconfigured to affect a material property of the mesoporous carbon-basedparticle, the material property further comprising any one or more of anelectrical conductivity, a wettability, or an ion conduction.
 20. Thecomposition of matter of claim 19, wherein the wettability is configuredto at least in part be affected by an electric charge associated withthe mesoporous carbon-based particle.
 21. The composition of matter ofclaim 1, wherein the plurality of interconnected pores is defined by oneor more dimensions ranging from 1 to 3 nanometers.
 22. The compositionof matter of claim 1, wherein any one or more of the graphene sheetsranges from between approximately 50 and 200 nanometers.
 23. Thecomposition of matter of claim 1, wherein the 3D hierarchical openporous structure is configured to be created independent of a binder.24.-30. (canceled)